The rheo-kinetics of thermoplastic polyurethane (TPU) formation was investigated in a measurement kneader at high temperatures. The TPU was made of a polyester polyol, methyl-propane-diol and a 50/50 mixture of 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI). The reaction proceeded according to a second order reaction for which the kinetic constants were determined by size exclusion chromatography (SEC) analysis. The activation energy was found to be equal to 61.3 kJ/mol, and the pre-exponential factor was equal to 2.18e6 mol/kg K. For the temperature range under investigation, the flow activation energy was equal to 42.7 kJ/mol, which is comparable to that of a linear polymer. This indicates that the hard segments are completely dissolved at the temperatures investigated. The initial part of the reaction was much faster than anticipated from the kinetic measurements. Diffusion limitations at higher conversions probably cause this decrease in reaction velocity. At longer reaction times, the molecular weight leveled off because of depolymerization. Therefore, additional experiments are necessary to describe the complete polymerization of thermoplastic polyurethane. (C) 2004 Society of Plastics Engineers.