Thermochemical Preference for C–C Bond Scission in an Isotactic Polypropylene Oligomer: A DFT-Based Study

Polypropylene (PP) waste, including microplastic debris, motivates molecular-scale studies of the intrinsic factors governing thermal degradation. In this work, the bond dissociation energies (BDEs) of C–C and C–H bonds were systematically evaluated in a finite isotactic polypropylene oligomer containing fifteen propylene repeat units, (–C₃H₆–)₁₅, using Density Functional Theory at the M06-2X/LANL2DZ level. Thermochemical corrections were evaluated at 873.15 K, a temperature relevant to pyrolysis studies. Within the selected oligomer model, C–C bonds exhibited lower BDE values (82.28–87.41 kcal·mol⁻¹) than C–H bonds (90.18–104.93 kcal·mol⁻¹), indicating a thermochemical preference for backbone scission. The lowest calculated BDE values were associated with specific tertiary carbon environments, including sites C24 and C28. A mixed-effects model identified bond type and carbon type as the principal factors associated with BDE variation, while principal component analysis summarized the covariation among the electronic and thermodynamic descriptors. These results provide a molecular-scale description of intrinsic scission tendencies within the selected PP oligomer and establish a basis for subsequent kinetic, catalytic, and experimental studies.