Radical Polymerization Behavior of Ethyl α–Naphthoyloxymethylacrylate

The polymerization of ethyl α-naphthoyloxymethylacrylate (ENMA) with dimethyl 2,2′-azobisisobutyrate (MAIB) in benzene was investigated kinetically and by means of ESR. Polymerization rate (R p) was given by Rp = k[MAIB]0.5[ENMA]1.7 (50°C). The overall activation energy of polymerization was estimated to be 58.4 kJ/mol. The actual polymerization system was found to involve ESR-observable propagating polymer radicals of ENMA. ESR determination of the polymer radical concentration allowed rate constants of propagation (k p) and termination (k t) to be estimated at 60°C: k p = 320 L˙mol−1˙s−1 k t = 3.7 × 105 L˙mol−1˙s−1. Dynamic thermogravimetry showed that the thermal degradation of poly(ENMA) begins at 340°C, and the residue at 500°C was only 4% of the initial polymer. Application of the Kelen–Tüdös method to the copolymerization results of ENMA (M1) and styrene (M2) at 50°C gave the following parameters: r 1 = 0.24 ± 0.01 and r 2 = 0.22 ± 0.01 giving Q 1 = 1.14 and e 1 = +0.78.