聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解

Synthesis and Non-isothermal Thermal Decomposition of Polydiphenyl(diphenylethynyl) Silane

以溴乙烷、二苯基二氯硅烷、苯乙炔为原料,通过格利雅反应合成二苯基二苯乙炔基硅烷单体(DPDPES),利用FTIR和~1H-NMR对单体分子结构进行表征。采用热聚合方法制备了聚二苯基二苯乙炔基硅烷树脂(PDPDPES),借助TG-DTG技术研究了PDPDPES的非等温热分解过程,运用模型法对热分解过程进行分析,建立动力学函数,推导出热分解机理,并应用非模型法对热分解机理函数进行验证。实验结果表明,6种分析方法得到的热分解活化能E_a=245.37kJ/mol,指前因子lgA=13.78s^(-1),机理函数式:f(α)=10/23·(1-α)·[-ln(1-α)]^(-1.3);g(α)=[-ln(1-α)]^(2.3)。

Diphenyldiphenylethynylsilane monomer （DPDPES） was synthesized with ethyl bromide, diphenyldichlorosilane and phenylacetylene by Grignard reaction.The molecular structure was characterized by FTIR and 1H-NMR spectroscopy.The polymer of polydiphenyl（diphenylethynyl）silane （PDPDPES） was also prepared by thermal polymerization.Non-isothermal thermal decomposition process of PDPDPES was studied with TG-DTG technology via model method to get thermal decomposition function and the corresponding mechanism which was further verified by model-free method.Results show that the apparent activation energy and the pre-exponential factor are about Ea=245.37kJ/mol and lgA=13.78s-1 obtained by six different kinetic methods, respectively.The mechanism of functions are f（α）=1023·（1-α）·[-ln（1-α）]-1.3 and g（α）=[-ln（1-α）]2.3.