Reaction Kinetic Modeling of the Synthesis of Polymers of Intrinsic Microporosity

Abstract Polymers of intrinsic microporosity porosity (PIMs) represent a versatile class of materials first discovered over 20 years ago. Despite extensive studies resulting in the optimization of their synthesis, the underlying reaction kinetics have never been the focus of research. This study presents a detailed examination of the reaction kinetics involved in the low‐temperature PIM‐1 synthesis, combining online reaction calorimetry with offline characterization techniques. A reaction kinetic model that describes both the initial deprotonation and the subsequent polycondensation of PIM‐1 is developed. Parameter estimation based on experimental data, followed by comprehensive sensitivity analysis, provides valuable insights into the synthesis process. This model can be applied to further optimize the synthesis process, enhancing both product properties and space‐time yield.