Monoesterification of styrene–maleic anhydride copolymers with alcohols in ethyl benzene: Catalysis and kinetics

A kinetic investigation on the monoesterification reaction of the maleic anhydride residue (MA) in styrene‐maleic anhydride copolymers with aliphatic alcohols was carried out in ethyl benzene solution. By comparison to classic catalysts such as tributylamine (TBA) and pyridine, 4‐dimethylaminopyridine (4DMAP) is by far the most effective catalyst for this reaction. While both general base and nucleophilic mechanisms contribute to the reaction catalyzed by TBA or pyridine, a nucleophilic mechanism prevails with 4DMAP. This reaction is reversible, and its chemical equilibrium constant decreases significantly with increasing temperature. Both kinetic and thermodynamic results showed that in the presence of 4DMAP, the forward and reverse reactions are second and first order, respectively. The existence of side reactions, reactivity of two styrene‐maleic anhydride copolymers of different MA contents as well as two aliphatic alcohols of different lengths are also addressed.