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Effect of dual functional ionic liquids on the thermal degradation of poly(vinyl chloride)

机译：双功能离子液体对聚氯乙烯热降解的影响

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The short-term thermal stability of PVC on addition of functional ionic liquids (ILs) based on phosphonium and pyridinium cations, and a docusate anion, was studied using FTIR, TGA-MS and TGA-FTIR. The thermal stability of PVC plasticized with these ILs is reduced and the activation energy for thermal degradation for the first step of PVC degradation lowered, relative to neat PVC. This feature is not dependent on the thermal stability of the IL itself, as their addition to neat PVC did not result in increased thermal stability of the resin. Analysis of the gases evolved during thermal degradation showed that there is no variation in the mechanism of PVC degradation in the presence of ILs, the only difference observed is that HCl is evolved at lower temperatures for PVC-ILs samples. The ILs had no effect on the second step of the thermal degradation of PVC. The decrease in the thermal stability of PVC-ILs is associated with two different effects: firstly, the anion weakens the Csingle bondH bond while the cation forms complexes and weakens the Csingle bondCl bond; second, the IL interaction with the polymer chains partly substitutes the interaction between the polymer chain and heat stabilizers (e.g. stearates) added to the PVC compound. In this way, the latter tends to be expelled from the bulk polymer, thus not being available for PVC stabilization at high temperature. Heat stabilizer migration is related to the solvating power of the ILs: the higher the solvating power, the higher the migration of heat stabilizer, the lower the thermal stability of the polymer.
机译：使用FTIR，TGA-MS和TGA-FTIR研究了添加基于phospho和吡啶鎓阳离子的功能性离子液体（IL）和多库酯阴离子后PVC的短期热稳定性。相对于纯净的PVC，用这些IL增塑的PVC的热稳定性降低，并且用于PVC降解第一步的热降解活化能降低。此功能不依赖于IL本身的热稳定性，因为将它们添加到纯PVC中不会导致树脂的热稳定性提高。对热降解过程中产生的气体的分析表明，在存在IL的情况下，PVC降解的机理没有变化，观察到的唯一区别是，PVC-ILs样品在较低的温度下释放出HCl。 IL对PVC热降解的第二步没有影响。 PVC-ILs热稳定性的下降与两种不同的作用有关：首先，阴离子削弱了Cingle键的H键，而阳离子形成了络合物，削弱了Cingle键的Cl键。第二，IL与聚合物链的相互作用部分替代了聚合物链与添加到PVC化合物中的热稳定剂（例如硬脂酸酯）之间的相互作用。这样，后者倾向于从本体聚合物中排出，因此不能用于高温下的PVC稳定化。热稳定剂的迁移与IL的溶剂化能力有关：溶剂化能力越高，热稳定剂的迁移就越高，聚合物的热稳定性越低。

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