Non-Isocyanate Polyurethane Featuring Programmable Functionality, Tunable Multiscale Porous Architecture, Good Reprocessability and Shape Memory Property via A Facile One-Pot Bottom-Up Strategy Under Ambient Conditions

Abstract

Polyurethanes (PUs) with porous architectures have diverse applications in different fields. However, their synthesis relies heavily on highly toxic isocyanate reactants and hazardous catalysts, posing environmental, health, and safety risks. In addition, the porous architectures of PUs are generally created by tedious top-down methods, increasing operational complexity and time inefficiency. In this study, we develop a facile one-pot bottom-up approach for synthesizing non-isocyanate polyurethanes (NIPUs) with both programmable chemical functionalities and tunable multiscale porous architectures across micro- to nanometer scales from catalyst-free reaction of polyamine, epoxide, and cyclic carbonate. This approach integrates in situ partial functionalization of polyamines by epoxides with a spontaneous phase separation of the evolving NIPU occurred during the polymerization of the partially functionalized polyamines with cyclic carbonates. A simultaneous edition of the chemical functionality of NIPU and engineering of the porous architectures of NIPU is achieved through a single, streamlined one-pot process. The developed strategy offers several advantages: ambient-temperature operation, elimination of toxic isocyanates and hazardous catalysts, precise control over both chemical functionality and porous architectures of NIPU, and inherently pure end products with good reprocessability and shape memory property. These merits position the methodology as a promising platform for synthesizing porous NIPUs tailored to meet the demands of biomedical, microelectronic, and sustainable packaging applications—fields where safety, structural precision, and process efficiency are paramount.