运用 TG-DTG技术研究了炔丙基改性酚醛树脂聚合物的非等温热分解过程,通过 Kissinger法和FWO 法获得聚合物分解的动力学参数,利用模型拟合法推测该聚合物的热分解机理,并用非模型拟合法对机理进行了验证。实验结果表明,该聚合物的T d5分解温度在390℃左右,800℃时残炭率在30％左右。7种动力学分析方法显示聚合物的热分解活化能为92．95 kJ/mol,指前因子lgA ＝4．71 s－1,n ＝2,分解符合二维扩散机理,对应的机理微分函数 f (α)＝(1－α)121－ (1－α)12[]－1积分函数 g (α)＝ 1－ (1－α)12[]2聚合物的热分解反应方程为 dα dT ＝5．14×104β?è???÷ exp －92．95×103 RT ?è???÷×(1－α)12× 1－ (1－α)12[]－1。
The non-isothermal thermal decomposition process of poly(propargyl modified novolac resin)(PPN) 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 FWO methods.The mechanism of thermal decomposition reaction of polymer was proposed by the model method and the obtained mechanism was further verified applying the non-model method.The results show that the Td5 temperature of the polymer was about 390 ℃ and the char yield was about 30% at 800 ℃.The activation energy,the pre-exponential factor and the order of the reaction (n)were about E=92.95 kJ/mol,lgA=4.71 s-1 and n=2.The thermal decomposition reaction mechanism followed the 3D diffusion control and the differential mechanism function f(α)=n(1-α)× [-ln(1-α)]1-1n The integral mechanism function g(α)= -ln(1-α) 1 n[ ] The corresponding reaction function was dαdT= 9.55 ×1016β?è? ??÷ exp -260.55 ×103RT?è? ??÷× 15 (1-α)×[-ln(1-α)]-4.
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