Understanding Rapid PET Degradation via Reactive Molecular Dynamics Simulation and Kinetic Modeling

As the demand for PET plastic products continues to grow,
developing
effective processes to reduce their pollution is of critical importance.
Pyrolysis, a promising technology to produce lighter and recyclable
components from wasted plastic products, has therefore received considerable
attention. In this work, the rapid pyrolysis of PET was studied by
using reactive molecular dynamics (MD) simulations. Mechanisms for
yielding gas species were unraveled, which involve the generation
of ethylene and TPA radicals from ester oxygen–alkyl carbon
bond dissociation and condensation reactions to consume TPA radicals
with the products of long chains containing a phenyl benzoate structure
and CO2. As atomistic simulations are typically conducted
at the time scale of a few nanoseconds, a high temperature (i.e.,
>1000 K) is adopted for accelerated reaction events. To apply the
results from MD simulations to practical pyrolysis processes, a kinetic
model based on a set of ordinary differential equations was established,
which is capable of describing the key products of PET pyrolysis as
a function of time and temperature. It was further exploited to determine
the optimal reaction conditions for low environmental impact. Overall,
this study conducted a detailed mechanism study of PET pyrolysis and
established an effective kinetic model for the main species. The approach
presented herein to extract kinetic information such as detailed kinetic
constants and activation energies from atomistic MD simulations can
also be applied to related systems such as the pyrolysis of other
polymers.