Optimization of the synthesis of polyhydroxyurethanes using dynamic rheometry

Polyhydroxyurethanes (PHUs) produced by the reaction between dicyclocarbonate and diamine groups are often presented as possible candidates to substitute for classical polyurethanes based on isocyanate precursors. In the literature, the synthesis of this class of polymers is often performed according to arbitrary conditions of time and temperature without any scientific justification. As such, the real potential of PHUs is probably not fully known. Numerous contradictions in previously published results seem to support this hypothesis. Our paper proposes two methodologies based on dynamic rheometry to determine optimized conditions for the synthesis of PHUs. The case of a PHU formed by the reaction between 1,10-diaminodecane and a dicyclocarbonate bearing a central aromatic group is described more precisely. The first approach consists of conducting various rheological experiments (kinetics, thermomechanical analyses) in situ on the reaction mixture. The second one retains the same technique to qualify the viscoelastic properties of PHUs synthesized according to various conditions. In this latter case, all samples show thermomechanical behaviour of amorphous thermoplastic polymers. But discrepancies are observed with regard to the value of the glass transition temperature and the existence or not of a rubbery zone. Comparison of these data with size exclusion chromatography results shows that these differences are direct consequences of the polymer molecular weight that can be predicted using macromolecular theory. The properties of the PHUs obtained after optimization of the polymerization reaction were compared with literature data in order to complete the evaluation of the efficiency of the rheological methodology. Copyright (C) 2012 Society of Chemical Industry