College of Chemical Engineering, Anhui University of Science and Technology, 232001 Huainan, China.
College of Chemical Engineering, Anhui University of Science and Technology, 232001 Huainan, China.
Waste Manag. 2021 Feb 15;121:52-58. doi: 10.1016/j.wasman.2020.11.019. Epub 2020 Dec 19.
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 × 10exp (-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.
钙皂和多元醇(季戊四醇)添加剂由于成本低、无毒性和安全性,正在取代或部分取代聚氯乙烯(PVC)热稳定剂中的有机锡。因此,从源头研究稳定增塑 PVC 的低温热氧化降解对于回收利用至关重要。本工作采用等温热重法研究了在 453-503 K 下空气气氛中具有优异耐热性的 PVC/钙皂/季戊四醇/有机锡软制品的热降解过程和等温变色。采用化学动力学方法对 PVC 热氧化降解过程的质量损失和时间进行单方程模型拟合,得到的动力学方程为:-ln(1-α)=3.83×10exp(-6834.4/T)t。当温度为 453-503 K 时,计算结果与实验数据基本一致,且与升温速率和温度变化无关。此外,在 468 K 空气气氛下测试了不同 PVC 材料的等温变色。结果表明,当测试材料为 PVC/钙皂/季戊四醇/有机锡时,变为完全黑化的热老化时间长于空白样品,表明 Sn、Ca 和季戊四醇络合物与 PVC 分子之间发生了强烈相互作用,抑制了氯化氢的释放。同时,为了回收 PVC 并防止其碳化,如果将温度设定为 486 K,则 PVC 的热氧化降解时间应小于 130 min。