Copolyperoxides of 2-(acetoacetoxy)ethyl methacrylate with methyl methacrylate and styrene; Synthesis, characterization, thermal analysis, and reactivity ratios

Copolyperoxides of 2-(acetoacetoxy)ethyl methacrylate (AEMA) with styrene (St) and methyl methacrylate (MMA) of different compositions have been synthesized in the presence of 2,2′-azobisisobutyronitrile as a free radical initiator under 100 psi oxygen pressure at 50 °C. The rates of oxidative copolymerization reactions are determined from the oxygen consumption (Δp) against time plot. Highly exothermic thermal degradations of these copolyperoxides are studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) and degradation products have been characterised by electron-impact mass spectroscopy (EI-MS). The NMR spectroscopy and EI-MS analysis confirm the alternating peroxy bonds in the main chain. The monomer reactivity ratios are computed by the Fineman-Ross and Kelen-Tüdös methods, using compositions obtained from 1H and 13C NMR analysis. These copolymers can potentially be used as polymeric initiators for the radical polymerization of vinyl monomers, autocombustible fuel. Also, the β-carbonyl moieties along the side chain of the copolyperoxides can be utilized to prepare degradable polyperoxide-metal complexes.