Prepolymers with propargylic terminal residues .1. Simulation of reaction mechanisms and kinetics on monofunctional models

We have undertaken the study of the kinetic and polymerization mechanisms of a series of monofunctional propargylic compounds, using H-1 and C-13 nuclear magnetic resonance, high performance liquid chromatography, Fourier transform infrared spectroscopy, and thermal analysis in the temperature range of 50-350 degrees C. The results obtained have shown that the reaction starts by intramolecular ring formation (Claisen rearrangement). Based on a set of consistent physicochemical data, a reaction mechanism for these systems and a kinetic model of polymerization in the molten state can be proposed, corresponding to the formation of the first species before the gel point. (C) 1997 Elsevier Science Ltd.