In this study, density functional theory (DFT) molecular modeling studies were performed to explore mechanisms underlying the interactions of cocatalysts in Ziegler–Natta olefin polymerization using a range of commercially available cocatalysts, namely, trimethylaluminum (in monomeric and dimeric form, Al2Me6), dimethylaluminum chloride (in monomeric and dimeric form, Al2Me4Cl2), and triisobutylaluminum. In this regard, after exploring structural and electronic features of cocatalysts, by steric maps and conceptual DFT, their interaction with possible impurities in hydrocarbon solvents and monomer feeds such as NH3, CH3OH, H2O, H2S, CO2, and O2 was considered. Then, activation of Ti species, adsorbed on the (110) and (104) surfaces, with the assistance of cocatalysts was studied as well. In this aspect, two possible reactions were investigated: (i) formation of first vacancy on Ti center and (ii) formation of first Ti–C bond by transalkylation reaction with cocatalysts. Finally, the effect of cocatalysts on the stereospecificity of Ti center adsorbed on the (110) surface was also taken into account by DFT calculations.

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