Cascading Retro-Diels–Alder Cycloreversion and Sydnone-Maleimide Based Double 1,3-Dipolar Cycloaddition for Quantitative Thermal Cross-Linking of an Amorphous Polymer Solid

A new approach to polymer cross-linking is investigated using a cascading cycloreversion of a maleimide-furan adduct and a double 1,3-dipolar cycloaddition between a sydnone and maleimide. The cross-linking proceeds quantitatively above 63 °C, despite the polymer possessing no observable glass transition temperature. The resulting polymer network possesses a high thermal stability (>300 °C) due to the irreversibility of the sydnone-maleimide cycloaddition, which releases CO2 during the cross-linking, driving the reaction. The rigid three-dimensional structure of the bis-maleimide-sydnone cycloadduct produced local free volumes in films, decreasing the dielectric constant of the material.