A Molecular Modeling Study on the Propagation in Free Radical Chain Oxidation of (B)PEI

Abstract

Air oxidation of PEI is a Free Radical Chain Autoxidation process, described as a process following the Basic Autoxidation Scheme with Initiation, Propagation and Termination as discriminating steps. Molecular Modeling was able to identify the most important propagation reactions. HO2(d) is the most likely candidate as the main oxidation chain carrying radical. α-H-abstraction from PEI α-amino hydroperoxides by HO2(d), leading to amide PEI repeat units and eventually to HO2(d) again, is the first step in Propagation. Apart from well-know propagation reactions, the reaction of PEI α-amino CH(d) radicals with H2O2 is of major importance, too, with an estimated contribution of ~50% to Propagation. Furthermore, it provides an explanation for the formation of NH3 and various imine PEI repeat units. PEI α-amino alkoxy radicals might contribute to some extent to Propagation and can lead to chain breaks in PEI and the formation of CO2. Amide and imine PEI repeat units contribute to ~90% of the fully oxidized PEI.

Keywords

• density functional theory
• Free Radical Chain Autoxidation
• Basic Autoxidation Scheme