Study of step‐growth polymerizations using epoxy‐carboxy reaction, 1. Study of the epoxy‐carboxy reaction on models in solvents of low or medium dielectric constants

Due to its importance in the field of block‐polycondensation and of chemical modification, we carried out an extensive study of the epoxy‐carboxy reaction on models. This papier is related to the reaction of benzoic acid with 1‐phenoxy‐2,3‐epoxypropane in the presence of a basic catalyst, N,N‐dimethyldodecylamine. It is carried out in low polar solvents (xylene, chlorobenzene, and o‐dichlorobenzene); essential kinetic parameters are reported. From studies carried out under stoichiometric or non‐stoichiometric conditions a general rate equation (υ = k [acid]0.5 [epoxy] [amine]) is obtained. Kinetic relations are the same, no matter what the catalyst is: dimethyldodecylammonium benzoate or free amine. From these kinetic data it results that the overall mechanism involves two steps.