采用无模型法对聚3,3-双叠氮甲基环氧丁烷（PBAMO）的热分解反应动力学进行了计算,并用热重-红外-质谱（TG-IR-MS）联用技术研究了其热分解反应产物。PBAMO表现出了独特的热分解过程,TG曲线中在210℃~270℃叠氮基团的分解失重之后没有第二个明显的失重台阶;PBAMO第一阶段的热分解活化能为150 kJ/mol,当分解率大于0.4时,活化能降为负值。TG-IR-MS结果表明,在叠氮基团分解时释放的热量加速了剩余氮原子的氧化还原过程,主要产物形式为NO,主链中的氧原子被消耗掉,从而导致了碳链骨架的大量残留。
Thermal decomposition kinetics of poly(3,3-bisazidomethyloxetane)(PBAMO) were studied by model-free method,and thermal decomposition products were measured using combination technology of thermogravimetry/infrared spectrum/mass spectrometry(TG-IR-MS) as well.PBAMO exhibits unique decomposition process: there is no obvious weight loss stage in the TG curves after the decomposition of azide group at 210 ℃~270 ℃.The activation energy is about 150 kJ/mol at the first stage of decomposition.However,the activation energy becomes negative when the conversion is more than 0.4.The results of TG-IR-MS show that heat release in the decomposition of azide group accelerates the oxidation process of the surplus nitrogen atom,and the main product is NO.Carbon chain residues are left over caused by the consumption of oxygen.
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