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

作　　者：谭德新[1] 徐远[1] 王艳丽[2] 疏瑞文[1] 邢宏龙[1] 

机构地区：[1]安徽理工大学化学工程学院,安徽淮南232001 [2]安徽理工大学材料科学与工程学院,安徽淮南232001

出　　处：《材料工程》2017年第7期77-83,共7页Journal of Materials Engineering

基　　金：国家自然科学基金(51477002;51303005);安徽省高校自然科学基金重点项目(KJ2013A087;KJ2013A095)

摘　　要：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.

关 键 词：聚二苯基二苯乙炔基硅烷树脂 模型法 非模型法 热分解机理 

分 类 号：O631[理学—高分子化学]