Mechanism and Kinetics of the Induction Period in Nitroxide Mediated Thermal Autopolymerizations. Application to the Spontaneous Copolymerization of Styrene and Maleic Anhydride

Recently we reported an experimental and theoretical (simulation) investigation on the mechanism of the induction period and the initial polymerization stages in the nitroxide mediated autopolymerization of styrene. In this paper we extend some of the results presented there and perform preliminary induction period experiments for the study of the mechanism and kinetics of the spontaneous copolymerization of styrene (S) and maleic anhydride (MA) in the presence of TEMPO and 4‐OH‐TEMPO. With even small amounts of MA (2% wt) the induction period is dramatically reduced by a factor of about 20 in comparison with the nitroxide‐mediated styrene autopolymerization at 120 °C. Our results suggest that the initiation mechanism involves a first step of reaction between S and MA. We speculate that this reaction is a Diels‐Alder cycloaddition followed by hydrogen ion through a monomer or TEMPO assisted homolysis to form a radical pair (monomer case) or a single radical (TEMPO case), which either initiates polymerization or is trapped by TEMPO depending on the conditions. Hall and Padias have studied similar electron donor‐acceptor co‐monomer pairs and favor the formation of a tetramethylene diradical as the initiating species for spontaneous copolymerization. In any case, the rate‐limiting step would be the initial reaction of S and MA. These induction experiments allow us to obtain an initial estimate of the order of magnitude for the kinetic constant of the rate‐limiting step, as 10−6 Lmol−1s−1.