聚十四烷基三苯乙炔基硅烷树脂的制备与热分解

Preparation and thermal decomposition of polytetradecyl(triphenylethynyl) silane resin

以镁条、溴乙烷、苯乙炔和十四烷基三氯硅烷为原料,通过格利雅反应制备了十四烷基三苯乙炔基硅烷(TTPES),采用红外和核磁共振光谱(~1H-NMR、^(13)C-NMR和^(29)Si-NMR)对其结构进行了表征。根据示差扫描量热法(DSC)确定了TTPES单体的固化工艺,由热聚合法制备了聚十四烷基三苯乙炔基硅烷树脂(PTTPES),利用TGDTG分析研究了PTTPES树脂的热分解行为,并采用Kissinger、Ozawa等6种方法研究了树脂的热分解动力学。结果表明,树脂的Td5为437℃,800℃残炭率高于43%。PTTPES树脂的热分解Ea为188.53 kJ/mol,指前因子A为1.27×10^(13)/s,得到了热分解动力学方程:(dα)/(dT)=(1.27×10^(13))/βexp ((-188.53)/(RT))·2/3α^(-1/2)。

The tetradecyl(triphenylethynyl)silane(TTPES)was synthesized via Grignard reaction of tetradecyl trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide. Its chemical structure was characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance spectroscopy(1H-NMR 13C-NMR,and 29Si-NMR). Its curing process was obtained by differential scanning calorimetry(DSC)and the corresponding polytetradecyl(triphenylethynyl)silane resin(PTTPES)was synthesized by thermal polymerization. The thermal decomposition behavior was analyzed by TG and DTG, and the thermal decomposition kinetics was studied by six well-known kinetic methods,i.e.,Kissinger,Ozawa. The results showed that resin′ s Td5 decomposition temperature was 437 ℃ and the char yield was over 43 % at 800 ℃. The activation energy Eaand the pre-exponential factor A was 188.53 kJ/mol and 1.27 ×10^13/s respectively. The thermal decomposition kinetic equation was as follows 1.27×10^13/βexp ((-188.53)/(RT))·2/3α^1/2.