Since its discovery in 1985, syndiotactic polystyrene (sPS) has aroused a keen interest due to its attractive properties. Indeed, its high melting point, high chemical and heat resistances, low dielectric constant and low permeability to gases make sPS a promising material from an industrial point of view. Catalytic systems used for styrene polymerization play a key role in polymerization activity and polymer tacticity. Last decade studies focused on new rare-earth based metallocene catalysts with a strong syndiospecificity. The aim of this contribution is to use a molecular modelling approach in order to improve catalyst design for styrene stereoselective polymerization. Developed theoretical calculation methodology (DFT) allows to take into account solvent effects. First insertion reactional profiles were computed, for styrene polymerization catalysed by {R2C(C5H4)(R’R’9-fluorenyl)}Ln(allyl), in order to investigate the origin of syndiospecifity. These results are consistent with previous gas phase calculations made for styrene homopolymerization. Then, the influence of the bulky substituents on the allyl ligand and on the fluorenyl ligand have also been studied by DFT to obtain further insights about the reactivity.

Substitution effects in highly syndioselective styrene polymerization catalysts based on single-component allyl ansa-lanthanidocenes: A theoretical study

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.