Mechanism of cationic ring-opening polymerisation of ε-caprolactone using metallocene/borate catalytic systems: a DFT and NCI study on chain initiation, propagation and termination.

ABSTRACT: We present a comprehensive DFT investigation on the cationic ring-opening polymerisation (CROP) of ε-caprolactone (CL) using zirconocene/borate catalyst systems. All possible pathways of the interaction between cationic species [Cp₂ZrMe⁺] and counteranions, [A^-] = [MeB(C₆F₅)₃]^- and [B(C₆F₅)₄]^-, were examined during chain initiation, propagation, and termination steps. The calculations reveal an active chain-end mechanism with O-alkyl bond cleavage of the polymerisation. The catalytic performance of the two counteranions is found to be identical, and they influence the initial process through stabilisation of the cationic species via non-covalent interaction

SUBMITTER: Meelua W 

PROVIDER: S-EPMC11008195 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature