Kinetics of thermal oxidative degradation of poly (vinyl chloride) containing Ca and Sn at low temperature

Calcium metal soap and polyol (dipentaerythritol) additives are replacing or partially replacing organotin in poly(vinyl chloride) (PVC) heat stabilizers due to their low cost, nontoxicity and safety. Therefore, investigating the low-temperature thermal oxidative degradation of stabilized plasticized PVC from the source is essential for recycling. This work uses isothermal thermogravimetry to investigate the thermal degradation process and isothermal discoloration of PVC/calcium metal soap/dipentaerythritol/organotin soft products with excellent heat resistance at 453-503 K and under air atmosphere. The chemical kinetics method is used to fit a single equation model of mass loss and time during the thermal oxidation degradation of PVC, and the kinetic equation obtained is: -ln(1 - α) = 3.83 × 10³exp (-6834.4/T)t. When the temperature is 453-503 K, the calculation results are basically consistent with the experimental data and are independent of the heating rate and temperature changes. In addition, the isothermal discoloration of different PVC materials was tested under air atmosphere at 468 K. The results show that when the test material is PVC/calcium metal soap/dipentaerythritol/organotin, the heat aging time to become completely blackened is longer than that of the blank sample, which indicates a strong interaction occurs between Sn, Ca and dipentaerythritol complexes and PVC molecules, inhibiting the release of hydrogen chloride. At the same time, in order to recover PVC and prevent it from carbonization, if the temperature is set to 486 K, the thermal oxidation degradation time of PVC should be less than 130 min.