Tailoring NIPUs: Exploring the role of various diacids in non-isocyanate polyurethane synthesis

In recent decades, numerous efforts have been dedicated to the investigation of eco-friendly non-isocyanate polyurethanes (NIPUs) as alternatives to conventional polyurethanes (PUs). Since isocyanates are classified by the EU as hazardous and toxic compounds, NIPUs offer a promising route to mitigate isocyanate-related health risks as well as other environmental concerns associated with traditional PU synthesis. In the present study, we report the synthesis as well as the detailed structural and thermal characterization of a new series of fully biobased non-isocyanate polyurethanes (NIPUs) based on aliphatic dicarboxylic acids of different chain lengths. The NIPUs were prepared via a two-step polyaddition reaction involving glycerol carbonate and diamine. Their synthesis enables a sustainable pathway to tailor NIPUs’ physicochemical properties via diacid structure control. Studies of their structure, thermal behavior and trends, morphological, and hydrolytic findings confirmed strong diacid chain length dependence on glass transition temperature (Tg ~13, 0, ‒5 and –23 °C), molecular weight, surface wettability, and enzymatic degradability. Short-chain diacids yielded NIPUs with rapid hydrolytic degradation, while their longer-chain analogs were hydrophobic and thermally stable. Contact angle measurements (~75–85°) also confirm these trends. The tunable properties position these materials among strong candidates for biomedical applications.