Abstract The thermal degradation of resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate) (BDP) has been studied by 31P NMR, Q-TOF, and GPC at normal and extreme heating conditions. The thermal degradation begins with the elimination reaction that generates reactive monomers and arynes. The aryne-bisphosphate adducts or their decomposition products were identified through Q-TOF analysis. Through the intertwined condensations, transesterifications, and elimination reactions, the reactive acid phosphates are formed and eventually convert the bisphosphates into volatile triphenyl phosphate, oligomeric aryl/acid polyphosphates, and non-volatile polyphosphoric acid. It is these reactions and products that provide the bisphosphates effective pathways for entry into the vapor phase or action in the condensed phase. The facility of these reactions, particularly the elimination reaction that is the initiation step, to occur is critical for the high efficiency of flame retardancy displayed by the bisphosphates. A thermal Melvin rearrangement of the bisphosphates to arylphosphonates has also been established.

中文翻译：

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芳基二磷酸酯的热降解机理和多磷酸酯的形成

摘要 用 31P NMR、Q-TOF 和 GPC 在正常和极端加热条件下研究了间苯二酚双（磷酸二苯酯）（RDP）和双酚 A 双（磷酸二苯酯）（BDP）的热降解。热降解始于产生反应性单体和芳烃的消除反应。芳炔二磷酸加合物或其分解产物通过 Q-TOF 分析进行鉴定。通过相互交织的缩合、酯交换和消除反应，形成活性酸式磷酸酯并最终将二磷酸酯转化为挥发性磷酸三苯酯、低聚芳基/酸式多磷酸酯和非挥发性多磷酸。正是这些反应和产物为二磷酸盐提供了进入气相或在冷凝相中起作用的有效途径。这些反应，特别是作为引发步骤的消除反应发生的便利性对于双磷酸盐显示的高效阻燃性至关重要。还建立了二磷酸酯到芳基膦酸酯的热梅尔文重排。