Breaking Down\nthe Building Blocks: Quantum Chemical\nAnalysis of Diels–Alder Reactions for Future Self-Healing and\nRecyclable Polymer Networks

Covalent adaptable networks (CANs) are a key component\nfor future\ndevelopment of sustainable materials. By modifying the Diels–Alder\n(DA) chemistry used as cross-links within these CANs, one can obtain\npolymers with tunable kinetic and thermodynamic properties. Given\nthe large number of possible diene/dienophile combinations, computational\nchemistry presents itself as an ideal platform to study the full DA\nenergetics. In this work, 130 DA reactions were scrutinized using\ndensity functional theory, with special attention for biobased components\nand <i>endo</i>/<i>exo</i> stereoisomerism. We\nfound that the Diels–Alder reaction can be conditioned for\na broad spectrum of applications, with bond formation and breaking\nat desired temperature ranges. Based on structural features and electronic\nnature, reactivity trends were studied to further enhance our understanding\nof the DA chemistry. Finally, for some interesting combinations, the\nkinetic and thermodynamic properties were translated to conversion\ncurves. This work serves as a guide for the smart selection of suitable\nDA chemistry for sustainable material applications.