In Situ Performic Acid Epoxidation of Polyfarnesene: Evidence of Oxirane Ring Instability and Its Impact on Multifunctional Polymer Composition

Polyfarnesene, a bio-based polymer, was epoxidized in situ using performic acid to investigate oxirane ring formation, stability, and the role of its bottlebrush architecture in the kinetics. The reaction reached a maximum epoxidation degree of ~20% after 6 h but underwent side reactions, producing hydroxyl and formic ester groups. FTIR and ¹H NMR revealed that ring opening began within the first hour, whereas residual unsaturated bonds persisted after prolonged reaction, owing to steric shielding by the polymer’s long C11–C13 side chains. Unlike smaller polydiene homologues, polyfarnesene exhibited slower ring-opening kinetics, retaining approximately 10% of oxirane groups after 20 h. GPC showed minimal molecular weight changes but an increase in polydispersity, confirming structural rearrangements without chain scission or crosslinking. DSC demonstrated that oxirane incorporation increased the T_g; however, side reactions reduced this effect by limiting chain mobility. These findings establish that the spatial constraints imposed by the bottlebrush architecture of polyfarnesene govern the reaction kinetics, restricting epoxidation efficiency and favoring esterification pathways. This interplay provides a basis for designing bio-based polymers with tunable thermal properties. Controlling the reaction environment to suppress side reactions is key to producing high-T_g epoxidized derivatives suitable for rubber technologies and sustainable materials.