Reprocessable Ferulic Acid-Based Nonisocyanate Polythiourethanes and Polyurethanes with High-Performance and Shape Memory Capabilities

The use of renewable raw materials to construct environmentally friendly, nontoxic, nonisocyanate polymer materials has been gaining attention. Here, we prepared ferulic acid epoxy (FAE) by directly reacting the lignin derivative ferulic acid with epichlorohydrin. It was used as a precursor to construct five-membered cyclic carbonate (CC) and five-membered cyclic dithiocarbonate (DTC) with CO2 and CS2, respectively. These cyclic carbonates are then cured with different amines to produce nonisocyanate polyurethanes (NIPUs) and nonisocyanate polythiourethanes (NIPTUs) with excellent properties. Ferulic acid contains a rigid aromatic ring structure, so the prepared nonisocyanate polymer materials have excellent mechanical properties, and the maximum tensile strength can reach 34.2 MPa. We compared NIPUs and NIPTUs in terms of their chemical structure, cross-link density, mechanical properties, and processing for remodeling. In addition, Due to the autoxidation of pendant sulfhydryl groups, disulfide bonds are present in the network structure of NIPTUs in addition to thionourethane. This endows NIPTUs with higher cross-link density, lower relaxation activation energy (Ea), and lower remodeling temperature (<140 °C). After thermocompression remodeling, the tensile strength of NIPTUs significantly increased due to the enhanced thermally induced formation of disulfide bonds. This study evaluates the potential for the direct synthesis of biobased aromatic NIPUs and NIPTUs based on ferulic acid, providing a simple route for the preparation of nonisocyanate polyurethanes and polythiourethanes using cyclic carbonates.