聚苯基三苯乙炔基硅烷的制备及热分解动力学

Preparation and thermal decomposition kinetics of poly (phenyl (triphenylethynyl) silane)s

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。

Using phenylethynylene and phenyltrichlorosilane as raw materials, phenyhri （ phenylethynyl ） silane [（ ph-C ≡ C ） 3= Si-ph] （PTPES）was synthesized by Grignard reaction. The molecular structure was characterized by means of Fouruier transform infrared （FT-IR） and nuclear magnetic resonance （NMR）. The polymer of poly （ phenyhri （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（ Ea ）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 de- composition reaction was first order reaction.