Kinetic Analysis of Thermal Decomposition of Polyvinyl Chloride at Various Oxygen Concentrations

Abstract

PVC plastic products are common combustible substances seen in fires, but their thermal degradation behavior under different oxygen concentrations has not been adequately studied. The thermal degradation behavior of PVC materials in atmospheres with different oxygen concentrations was analyzed via thermogravimetric–Fourier transform infrared spectroscopy (TG-FTIR). The TG results show that the thermal degradation process of PVC under a non-oxygenated atmosphere occurred in two stages, and the activation energies of the two stages were 130–175 KJ mol−1 and 230–320 KJ mol−1, respectively; under the oxygenated atmosphere, the thermal degradation process occurred in three stages. The activation energies of the three stages were 130–175 KJ mol−1, 145–510 KJ mol−1 and 75–190 KJ mol−1, respectively. And the reaction mechanism of the second stage of thermal degradation was changed from D-ZLT3 to En by the higher oxygen concentration. Infrared spectroscopy (FTIR) was used to analyze the pyrolysis process of PVC in the non-oxygenated atmosphere, and the eight major components were as follows, in descending order according to amount released: C-H stretching > HCl > C-Cl stretching > H2O > CO2 > C-H bending > C-H aliphatic bending > CH2. For the reaction of PVC at an oxygen concentration of 7%, the nine major components, in descending order according to amount released, were as follows: CO2 > HCl > H2O > CO > C-H stretching > C-Cl stretching > C-H aliphatic bending > C-H bending > CH2. For PVC reactions at oxygen concentrations of 14% and 21%, the five major components, in descending order according to amount released, were CO2 > HCl > CO > C-Cl stretching > H2O.