新型特种工程塑料聚芳醚砜酮和聚芳醚砜热分解动力学及寿命预测

采用逐步聚合方法制备了新型特种工程塑料含二氮杂萘酮结构的聚芳醚砜酮［PPESK(1/1)］和聚芳醚砜(PPES).利用热失重(TGA)分析仪，氮气氛围中，多重加热扫描速率下的不定温法对PPESK(1/1)及PPES进行热分解动力学研究.根据Satava法得出，聚合物PPESK(1/1)分解反应机理为随机成核和随后生长，反应级数n=1;而聚合物PPES的热分解反应机理为相界面反应模式，反应级数n＝2.同时采用经典动力学方程Friedman、Kissinger-Akahira-Sunose(KAS)及Ozawa方程计算了热分解动力学参数(E_a，lnZ).重点考察升温速率、不同酮/砜比对PPESK（1/1）热稳定性影响，并且根据得到的动力学参数推测其在高温使用条件下的使用寿命及对热分解反应过程中“动力学补偿效应”（KCE）进行分析.

Kinetics of thermal degradation of special engineering thermoplastics PPESK and PPES and life estimation

New special engineering thermoplastics poly (phthalazinone ether sulfone) (PPES) and poly (phthalazinone ether sulfone ketone) ［PPESK(1/1)］ containing phthalazinone were synthesized by step-polymerization. The kinetics of thermal degradation of PPES and PPESK(1/1) in nitrogen were studied at several heating rates by thermogravimetry analysis (TGA). According to the Satava method, the thermal degradation mechanism of PPESK(1/1) was randomly nucleating and nucleus growth, and the order of reaction n=1.The thermal degradation mechanism of PPES, however, was phase boundary controlled reaction and the order of reaction n=2.The kinetic parameters, including the energy of activation and frequency factor of degradation reaction for PPES and PPESK(1/1) were analyzed by the Friedman, Kissinger-Akahira-Sunose(KAS) and Ozawa methods. The aim of this work was to study the effects of heating rate and the ratio of ketone/sulfone on thermal degradation and life estimation. On the basis of kinetic parameters, the lifetime for high temperature was calculated and the ‘Kinetic Compensation Effects’(KCE) in the thermal degradation process was analyzed.