The thermal decomposition behavior of poly[3,3-bis(ethoxymethyl)oxetane] (polyBEMO) was examined and compared to the decomposition of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (polyTHF). Differential scanning calorimetric (DSC) studies as a function of heating rates and at constant temperature as a function of time yielded activation energies of 45–50 kcal/mol, characteristic of polyether decomposition. First-order decomposition kinetics were found. The reaction is endothermic, with a heat of decomposition of 18.6 kcal/mol. Effusion mass spectroscopy on polyBEMO showed major peaks at 112, 140, 168, and 174 amu. A mechanism is proposed in which the thermal scission of the ether bonds in both the polymer chain and in the appendanges initiates the decomposition. The main decomposition reaction for polyBEMO can be written as where the appendages and main chain are cleaved in an unknown order.
