Kinetics and thermodynamics of thermally reversible polymers: Based on the furan-maleimide DA reaction

The diene-dienophile pair furan-maleimide is a popular choice in the design of thermally reversible or self-healing polymers based on the Diels-Alder (DA) reaction. This thesis contributes fundamental insights that can be used to tailor polymer properties for specific applications and examines how to cross-link reactants in the solvent efficiently. Novel methods are introduced to analyze the kinetics and mechanisms of reversible reactions by combining Differential Scanning Calorimetry (DSC) measurements and a series of models for cross-linked furanic polyketones with bis-maleimides. Furthermore, the limitations of atomistic simulations of such systems are examined systematically to propose ways in which the DA reaction can be captured accurately, allowing for the tailoring of reversible polymer properties. Finally, a new method is presented that can be used to calculate phase diagrams of organic and polymeric liquid mixtures via the UNIQUAC model implemented in the CALPHAD method, which is crucial to study the solubility of reactants in the solvent.