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通过热重分析研究了新型三元共聚物聚碳酸亚丙酯马来酸酐(PPCMA)在不同升温速率下的热分解动力学.设计并引入一种新的计算方法,非线性约化法(NLA),对共聚物热分解过程中的表观活化能进行了计算.研究发现,虽然用非线性约化法计算的表观活化能相对误差值稍大于用传统计算方法Flynn-Wall-Ozawa(FWO),Tang和Kissinger-Akahira-Sunose(KAS)计算的相对误差值,但其分析合理且计算过程更为简便.此外,固态反应模型拟合方法计算结果表明,共聚物的热分解过程对应多个反应机理.整个热分解过程,表观活化能值处于70-135kJ·mol-1之间,指前因子处于5.24×104-9.89×107min-1之间.同时,通过对表观活化能值的比较,初步解释了聚碳酸亚丙酯(PPC)与PPCMA热解温度差异的原因.
The thermal decomposition kinetics of the novel terpolymer polypropylene carbonate maleic anhydride (PPCMA) at different heating rates was studied by thermogravimetric analysis. A new calculation method was introduced and a nonlinear reduction method (NLA ), The apparent activation energy of the copolymer during thermal decomposition was calculated.It was found that although the relative error of apparent activation energy calculated by nonlinear reduction method is slightly larger than that calculated by traditional calculation method Flynn-Wall-Ozawa (FWO ), Tang and Kissinger-Akahira-Sunose (KAS), but the analysis is reasonable and the calculation process is more convenient. In addition, the calculation results of the solid state reaction model fitting method show that the thermal decomposition process of the copolymer corresponds to a number of Reaction mechanism.The apparent activation energy of the whole thermal decomposition process was in the range of 70-135kJ · mol-1 and the pre-exponential factor was in the range of 5.24 × 104-9.89 × 107min-1 .At the same time, The reasons for the difference in pyrolysis temperature between PPC and PPCMA are explained.