This work is dedicated to Dr. Alain Michel for his retirement and in memory of Prof. Morand Lambla. Dr. Michel and Prof. Lambla were the pioneers of the development of reactive processing in FranceThe review is devoted to the fundamental aspects of the reactive processing of thermoplastic polymers. First of all, some reactive processing examples, including polymer grafting (vinyl silane, maleic anhydride) and/or functionalization, bulk polymerization (urethane, lactams, acrylate, e-capolactone), polyester modification and new copolymers synthesis, are presented. From a fundamental point of view, the review covers the state of the art in the domains of rheology (specifically modelling of rheo-kinetics), diffusion and mixing in highly viscous reactive or non reactive media. Finally, 1, 2 and 3-D simulation of the reactive extrusion process in twin-screw extruder is reported at the end of the review.

Ring-opening polymerization of -caprolactone initiated by titanium n-propoxide Ti(O-n-Pr) 4 was compared to the one initiated by titanium phenoxide or Ti(OPh) 4 . Polymerization was confirmed to proceed via a coordination-insertion mechanism for both initiators after end groups analysis by 1 H and 13 C NMR (nuclear magnetic resonance) spectroscopy. Bulk polymerization at 100 °C and with a M 0 /I 0 (monomer/initiator ratio) equal to 300 was studied and compared with both initiators. The polymerization with Ti(OPh) 4 exhibits a slower kinetic of reaction and the polymer synthesized an higher number-average molecular weight and higher polydispersity than with Ti(OPr) 4 . These results are consistent with evolution of the average number of active aryloxide groups per initiator (N aag ) during polymerization for this initiator. Indeed, N aag determined by 1 H NMR increases gradually during the polymerization to 2 for around 70% conversion and then decreases at the end of the polymerization and even over the time required for total conversion. This decrease of N aag at the end of the conversion may be explained by important transesterification reactions with phenoxyl end groups of the polymer, which lead to the formation of larger poly( -caprolactone) chains. That is consistent with the increase in the number-average molecular weight of the polymer beyond the end of the conversion. The rheological study also confirms this result.