Quantum Chemical Simulation of Phenol-Formaldehyde Resin Carbonization in the Presence of Phosphoric Acid: Computational Evidence of Michaelis–Arbuzov-Type Reaction

Abstract

Quantum-chemical semiempirical simulation of phenol-formaldehyde resin carbonization was performed by PM6 method, resulting in atomic level models of neat and Pdoped disordered carbon structures. Mechanisms of curvedplane carbon fragments formation from postpolymeric chains is discussed, supported by change in statistic characteristics of the clusters. Transformation of phosphoric esters to phosphonates by Michaelis−Arbuzov-type reaction is described.

Thermal stability of phenolic resin: new insights based on bond dissociation energy and reactivity of functional groups

“…16,17,20 Molecular simulation techniques are effective and efficient in revealing the structural-thermal stability relationship of PR. For example, Jiang et al 21 and Qi et al 22 used the ReaxFF molecular dynamics method to track the initial pyrolysis paths, Bauschlicher et al 23 and Bian et al 24 calculated the BDE of the backbone bonds through density functional theory (DFT), Khavryuchenko et al 25 adopted the semi-empirical methods (PM7) to model the carbonization of PR. Among the molecular simulation methods, DFT has gained immense popularity over the past few decades due to its high computational efficiency and accuracy.…”