聚苯基三苯乙炔基硅烷的制备及热分解动力学

摘要

Using phenylethynylene and phenyltrichlorosilane as raw materials,phenyltri (phenylethynyl) silane [(ph-C ≡ C) 3-Si-ph] (PTPES)was synthesized by Grignard reaction.The molecular structure was characterized by means of Fournier transform in-frared (FT-IR) and nuclear magnetic resonance (NMR).The polymer of poly (phenyltri (phenylethynyl) silane) s was prepared by thermal polymerization with high char yield.The Td5 temperature of the polymer was about 570 ℃ and the char yield was about 75％ at 800 ℃ and the corresponding thermal decomposition kinetic parameters,such as activation energy(E,)and the order of the reaction(n) were also obtained according to the Kissinger and Ozawa methods by TGA-DTG.The results show that the Ea values were 295.82 kJ/mol and 262.70 kJ/mol by two methods,respectively.The reaction order was 0.96 by Crane equation and the decomposition reaction was first order reaction.%以苯乙炔和苯基三氯硅烷为原料,通过格氏反应制备了可反应型苯基三苯乙炔基硅烷单体,利用红外、核磁对其结构进行了表征.以此为原料,通过热聚合法制备了高残炭率的含硅芳炔树脂,该树脂的Td5分解温度约570℃,800℃时聚合物的残炭率约75％.利用TGA-DTG研究了该聚合物的热分解动力学,并计算了相应动力学参数.用Kissinger法和Ozawa法求得的聚合物热分解活化能分别为295.82 kJ/mol和262.70 kJ/mol；用Crane法求得聚合物的热分解反应级数为0.96,反应近似为一级反应.