聚苯基三苯乙炔基硅烷树脂的非等温热分解过程研究∗

摘要

借助 TG-DTG 技术研究了聚苯基三苯乙炔基硅烷树脂(PPTPES)在氮气气氛中不同升温速率下的热分解行为,利用模型拟合法和非模型拟合法求出了聚苯基三苯乙炔基硅烷树脂热分解反应动力学三因子及分解机理函数.计算结果表明,7种分析方法得到的 PPTPES 的平均热分解活化能为 E ＝252．76 kJ/mol,指前因子 lgA ＝13．93,反应级数 n ＝3,机理函数微分式为f (α)＝13(1－a )[－ ln(1－a )]积分式为g (α)＝[－ ln(1－α)]3－2反应遵循随机成核和随后生长机理.%The non-isothermal thermal decomposition process of poly (phenyltri (phenylethynyl )silane )s (PPTPES)in a nitrogen atmosphere was studied with TG-DTG technology,applying the model method com-bined with model-free method to get kinetic triplet and the mechanism of thermal decomposition reaction of PPTPES.The results obtained from 7 different methods show that the activation energy and the pre-exponential factor were E =252.76 kJ/mol,lgA =13.93 and n =3.The reaction differential function was f (α)= 1 3 (1 -a )[- ln(1 -a )]-2 and the integral mechanism function was g (α)=[- ln(1 -α)]3 and the reaction followed the random nucleation and growth mechanism.