Reactions in solid state within polyurethanes. Kinetics and postcure reaction mechanism in casting polyurethane elastomers

摘要

The solid state postcure reaction mechanism of polyurethane elastomers (PU) synthesized using a relatively small excess (up to 10%) of isocyanate was studied. The postcure process succeeds especially with the assistance of atmospheric humidity and, its process velocity depends on PU sample thickness. The polymer network is consolidated mainly by the formation of a new urea group. The formation of allophanate, uretidinedione, and isocyanurate groups and possible reticulations by the intermediary amine groups formed, play only a secondary role in the studied conditions. Kinetic equations regarding the postcure evolution were followed by means of the changes in mechanical properties. The evolution of the process was correlated to different kinetic measurements regarding the elementary processes involved like the consumption of NCO groups, absorption of water from the atmospheric humidity, and desorption of CO2 resulted during the formation of urea group. The CO2 desorption appears to be the slowest dynamic process. [References: 36]