Structure-property relationships in polyhydroxyurethanes produced from terephthaloyl dicyclocarbonate with various polyamines

This article focuses on the synthesis and characterization of polyhydroxyurethanes (PHUs) obtained from the reaction between bis[(2-oxo-1,3-dioxolan-4-yl)methyl]benzene-1,4-dicarboxylate (DCter) and various diamines (aliphatic, cycloaliphatic and oligomeric) or polyamines (diethylenetriamine (DETA) and diethylenetetramine (TETA)). The temperature and time conditions associated with each step-growth polyaddition were defined by rheological tests directly performed on the reactive mixture. The chemical structures of DCter-based PHUs containing primary and secondary alcohol groups were characterized using Fourier transform infrared spectroscopy. Differential scanning calorimetry experiments were performed on the various PHUs in order to investigate the influence of the chemical structure of the amines on the thermal properties of the polymers. Two different kinds of PHUs were obtained. On the one hand, the use of diamines led to thermoplastic polymers with a glass transition temperature (Tg) ranging from 4 to 78 degrees C depending on the flexibility of the diamine involved in the reaction. The hierarchy based on PHU Tg could be verified using the Van Krevelen methodology. On the other hand, PHUs produced from polyamines TETA and DETA were found to be insoluble and infusible due to the creation of polymeric networks. The DCterDETA polymer had a higher Tg revealing a probable difference in the reactivity of primary and secondary amine groups. Copyright (c) 2012 Society of Chemical Industry