Catalyst Activation and Chain Transfer Agents in Metallocene Catalysts for Ethylene Polymerization: A Computational Investigation

Abstract

AbstractA density functional theory (DFT) study has been carried out to investigate the effect of various cocatalysts/chain transfer agents (such as Al(R)3, Mg(R)2, (R)Mg(Cl), Zn(R)2, (R)Zn(Cl), B(C6F5)3, and Al(C6F5)3, here, R=alkyl group) on catalyst activation and ethylene polymerization including chain transfer steps using (CpR, R’)2M(Cl)2 (M=Zr, Hf and R, R’=alkyl group) metallocenes. Initially, the catalyst alkylation step (where one of the chlorine atoms of the catalyst is replaced by an alkyl group of the cocatalyst) has been studied using the Al(Me)3, Mg(Me)2, (Me)Mg(Cl), Zn(Me)2, and (Me)Zn(Cl) moieties, and it was observed that the AlMe3 species is more effective for the alkylation step. Furthermore, a modification in the metallocene, such as (CpR, R’)2Zr(Cl)2, where R and R’=H, Me, Et, n‐propyl, iso‐propyl, iso‐butyl, tert‐butyl, and different combinations of those, has been performed to evaluate the effect of different alkyl substituents on the alkylation process, whereby it was found that the mono‐substituted metallocene favors the alkylation in comparison to bi‐substituted metallocene. Moreover, a detailed fundamental understanding of the ion pair formation step was gained by incorporating various steric and electronic factors of different alkyl groups, including fluorinated alkyl group bound on the Cp ligand. These results suggest that only B(C6F5)3 and Al(C6F5)3 activators could form the ion pairs by abstracting a methyl group from the metallocene. Additionally, the ethylene polymerization has also been investigated using B(C6F5)3 or Al(C6F5)3 cocatalyst, where B(C6F5)3 was found to be more effective towards polymerization. Furthermore, the Al(Me)3, Mg(R)2, (Me)Mg(Cl), Zn(R)2, and (Me)Zn(Cl) species have been employed as chain transfer agent (CTA). It has been observed that the magnesium‐ and zinc‐based species are more likely to behave as CTAs, and this process can be improved by changing the alkyl substituents on them. These chemical calculations shed light on catalyst alkylation and ethylene polymerization, including the chain transfer process, in metallocenes.