Gas phase product evolution during high temperature pyrolysis of PTFE: Development of ReaxFF simulation protocol

The formation of products of incomplete destruction (PIDs) from fluoropolymer incineration is poorly understood and it is imperative to environmental impact studies. The lack of analytical standards limits the experimental approaches targeting product analysis. To navigate this challenge, computational modeling of the thermal degradation of fluoropolymers provides simulated product distributions. However, it is essential to benchmark reactive forcefields to accurately simulate fluoropolymer pyrolysis. The present work describes a protocol to perform accurate simulations of the thermal degradation of fluoropolymers to probe the PIDs. The ReaxFF force field was applied to reproduce the experimental bulk density and glass transition temperature of polytetrafluoroethylene (PTFE). The benchmarked methodology developed has been extended to provide simulated product distributions and mechanistic insights which are in excellent agreement with primary literature. On the basis of our simulated data, we observe a degradation mechanism that proceeds through three primary steps: 1) initiation of random backbone cleavage, 2) C2F4 unzipping through β–scission (as opposed to CF2 unzipping), and 3) secondary product formation. An extension of the developed protocol has the potential to simulate the thermal degradation of non-polymeric per- and polyfluoroalkyl substances (PFASs) in addition to long-chain fluoropolymers.