Fast Bulk Depolymerization of Polymethacrylates by ATRP

Fast bulk depolymerization of poly(n-butyl methacrylate) and poly(methyl methacrylate), prepared by atom transfer radical polymerization (ATRP), is reported in the temperature range between 150 and 230 °C. Depolymerization of Cl-terminated polymethacrylates was catalyzed by a CuCl2/TPMA complex (0.022 or 0.22 equiv vs P-Cl) and was studied using TGA, also under isothermal conditions. Relatively rapid 5–20 min depolymerization was observed at 230 and 180 °C. The preparative scale reactions were carried out using a short-path distillation setup with up to 84% depolymerization within 15 min at 230 °C.