Data Sheet 1_Investigation of polyurethane pyrolysis characteristics using reactive force field molecular dynamics.docx

Polyurethane (PU) pyrolysis characteristics were investigated using reactive force field molecular dynamics simulations to reveal the product distribution and thermal decomposition mechanisms. A PU molecular model was constructed and simulated its pyrolysis process at 1,500–3,000 K, analyzing potential energy changes, product species, carbon-containing component distribution, main gas products, main intermediate products and initial cleavage pathways. At 1,500 K, PU mainly decomposes into NHCOO and CH2 fragments, with concurrent gas release. At 1,800–2,100 K, aromatic amines, olefins, and gases (including CO2, CO, and NH3) are formed through radical recombination. At higher temperatures (2,400–3,000 K), carbon rearrangement is promoted, yielding dense C40+ species alongside persistent gases. The results show that PU pyrolysis initiates with the C-O-C bond cleavage of the NHCOOCH2 group, generating NHCOO and CH2 fragments, and this cleavage occurs via a homolytic pathway. The dynamic competition between main chain scission and radical recombination drives the complex pyrolysis network, with temperature governing product diversity. This work provides microscopic insights into PU thermal degradation, supporting applications in fire safety assessment and material recycling.