Pyrolysis and Pore Formation of Crosslinked Polystyrene‐ <i>Block</i> ‐Polybutadiene‐ <i>Block</i> ‐Polystyrene for Ordered Mesoporous Carbon Synthesis

ABSTRACT Thermoplastic elastomers (TPEs) have recently emerged as a class of promising precursors of ordered mesoporous carbons (OMCs) due to their low cost and broad availability. Despite understanding their reaction‐induced morphological changes, the fundamental pyrolysis kinetics of crosslinked TPEs remain poorly understood. In this study, we systematically investigate the pyrolysis behavior and pore formation mechanisms of sulfonated polystyrene‐ block ‐polybutadiene‐ block ‐polystyrene (SBS) using thermogravimetric analysis coupled with mass spectrometry (TGA‐MS), nitrogen physisorption measurements, and model‐free kinetic analysis. TGA‐MS results reveal a multi‐stage thermal decomposition process characterized by distinct thermal transitions and volatile product evolution. Nitrogen physisorption measurements demonstrate the development of mesoporosity and surface area with increasing pyrolysis temperature, identifying critical thermal windows for mesopore formation. Furthermore, kinetic modeling of the pyrolysis process was used to determine the apparent activation energies for the cleavage of aromatic and unsaturated moieties. These findings can provide important mechanistic insights for material and process design for producing OMCs via direct pyrolysis of commercially available TPEs.