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本文报道在4.1型示差精密热天平上装配了微分单元,组成热重-微商热重(TG-DTG)联用装置用于研究聚三氟氯乙烯在空气中的热裂解动力学过程,并运用几种不同的动力学处理方法所求得的结果来评价各种动力学理论的优缺点和说明聚三氟氯乙烯反应程度在5—95％的整个过程中活化能的变化情况。同时根据裂解程度与能量、裂解速率的关系以及裂解产物结构的鉴定,提出了聚合物无规热裂解机理,解释了迄今文献上所报道的裂解产物的结构。结果还证明了Errede提出的键离解能经验公式不适用于聚三氟氯乙烯的裂解机理。
In this paper, we report the differential thermal cell assembly on the 4.1 Differential Precision Thermometer, which is composed of a TG-DTG unit for the pyrolysis kinetics of polychlorotrifluoroethylene in the air. The results obtained from several different kinetic treatments were used to evaluate the strengths and weaknesses of various kinetic theories and to illustrate the changes in activation energy throughout the 5-95% course of the polychlorotrifluoroethylene reaction. At the same time, according to the relationship between the degree of pyrolysis and the energy, the rate of pyrolysis and the identification of pyrolysis products, the mechanism of random pyrolysis of the polymer was proposed, and the structure of the pyrolysis products reported so far was explained. The result also proves that the experiential formula of bond dissociation energy proposed by Errede does not apply to the cleavage mechanism of polychlorotrifluoroethylene.