1 research outputs found
Understanding and Optimizing the Behavior of Al- and Ru-Based Catalysts for the Synthesis of Polyisobutenyl Succinic Anhydrides
Polyisobutenyl succinic anhydrides (PIBSAs) are an important
class
of chemicals in the automotive industry due to their wide use in lubricant
and fuel formulations. However, the synthesis of these molecules takes
place at elevated temperatures through the ene reaction between maleic
anhydride (MAA) and polyisobutylene (PIB). Lewis acid catalysts (e.g.,
AlCl3) have been shown to facilitate PIBSA synthesis by
lowering the activation energy of the reaction; however, the desorption
of the final product (PIBSA) from the catalyst can be highly endergonic.
Herein, we demonstrate ligand engineering strategies to optimize the
performance of Al- and Ru-based catalysts by combining first-principles
calculations with kinetic modeling. We discover that alkyl chlorides
such as the EtAlCl2 retain relatively low activation barriers
like AlCl3, while lowering the desorption energy of the
final product (PIBSA). In addition, we address metal oxidation state
and ligand effects on the ene reaction performance of Ru-based catalysts.
We demonstrate that depending on the metal oxidation state and type
of ligands there is a competition between concerted and stepwise mechanisms.
We uncover a Ru(II) catalyst, RuCl2·2H2O, exhibiting enhanced activity but suffering from low stability.
Overall, our work identifies catalysts of industrial importance that
can reduce the energy input required for intensified processes and
highlights challenges associated with catalyst performance