利用热重-微分热重分析技术研究了自制的双酚芴乙二胺苯并噁嗪树脂在氮气气氛中的热分解动力学,通过Kissinger法和Ozawa法对该树脂进行动力学分析,求出相关动力学参数。利用模型拟合法推测双酚芴乙二胺苯并噁嗪树脂的热分解机理,并用非模型拟合法进行验证。结果表明,双酚芴乙二胺苯并噁嗪树脂的热分解平均活化能及指前因子分别为E=260.55 kJ/mol;lgA=16.98 sv^-1。双酚芴乙二胺树脂热分解过程符合随机成核和随后生长机理,其分解反应微分函数为f(α)=n(1-α)×[-ln(1-α)]1^-1n;积分函数为g(α)=[-ln(1-α)]^1/n,其中n=1/5,对应的热分解反应方程为dα/dT=(9.55×10^16/β)exp(-260.55×10^3/RT)×1/5(1-α)×[-ln(1-α)]^-4。
The non-isothermal thermal decomposition process of bisphenol fluorene diamine benzoxazine resin was studied with TG-DTG technology.The corresponding kinetic parameters such as activation energy(E)and pre-exponential factor(A)were obtained according to the Kissinger and Ozawa methods. A dynamic function and the mechanism of thermal decomposition reaction of resin were proposed by the model method and the corresponding energies were further verified applying the model-free method.The results show that the activation energy,the pre-exponential factor and the order of the reaction( n) are about E=260.55 kJ/mol,lgA= 16.98 and n=1/5,respectively.The differential mechanism function is f(α)=n(1-α)×[-ln(1-α)]1^-1n and the integral function is g(α)=[-ln(1-α)]^1/n. The thermal decomposition reaction mechanism follows the random nucleation and subsequent growth and the corresponding reaction function is:dα/dT=(9.55×10^16/β)exp(-260.55×10^3/RT)×1/5(1-α)×[-ln(1-α)]^-4.