对甲苯基三苯乙炔基硅烷的合成及其固化动力学研究  

Synthesis and curing kinetics of para-tolyltriphenylacetylene silane

作　　者：唐晓敏 曾佳欣 李舒平 刘美怡 谭德新 TANG Xiaomin;ZENG Jiaxin;LI Shuping;LIU Meiyi;TAN Dexin(School of Chemistry and Chemical Engineering,Lingnan Normal University,Zhanjiang 524048,China)

机构地区：[1]岭南师范学院化学化工学院,湛江524048

出　　处：《固体火箭技术》2022年第4期623-630,共8页Journal of Solid Rocket Technology

基　　金：广东省科技创新战略专项基金(2018A01005)。

摘　　要：为进一步提高对甲苯基三苯乙炔基硅烷(p-TTPES)耐热稳定性,通过对甲苯基三氯硅烷与苯乙炔进行Grignard反应合成p-TTPES,利用核磁共振波谱(NMR)和红外光谱(FT-IR)对其分子结构进行表征,采用差示扫描量热法(DSC)对单体的固化行为进行分析,并利用多重线性回归的计算方式,获得p-TTPES固化动力学模型。实验结果表明,等温DSC分析求得p-TTPES的反应活化能E_(a)为153.89 kJ/mol,指前因子A为5.25×10^(12) s^(-1),固化反应级数m+n约为2.0,反应与自催化模型相符;由非等温DSC曲线,借助Kissinger、Ozawa和Flynn-Wall-Ozawa动力学分析方法,求得p-TTPES的反应活化能分别为165.70、167.54、165.94 kJ/mol,指前因子A为2.76×10^(13) s^(-1);树脂氮气中5%热失重温度(T_(d5))超过460℃,800℃下树脂的残炭率为74%;结合DSC分析和TG分析表明,芳炔单体取代基碳原子数相近或相同时,结构变化对单体反应活化能影响很小,对树脂热稳定性影响较大。In order to further improve the thermal stability of para-tolyltri(phenylethynyl)silane monomer(p-TTPES),the p-TTPES was synthesized by Grignard reaction of phenylacetylene and para-tolylchlorosilane,its molecular structure was characterized by nuclear magnetic resonance spectroscopy(NMR)and fourier transform infrared spectroscopy(FT-IR).The curing behavior of monomer was analyzed by differential scanning calorimetry(DSC)and the p-TTPES curing kinetics model was also obtained by using the calculation method of multi-linear regression.The experimental results show that the reaction activation energy(E_(a))of p-TTPES is 153.89 kJ/mol obtained by isothermal DSC analysis,and the pre-exponential factor(A)is 5.25×10^(12) s^(-1).The curing reaction order(m+n)was about 2.0,which was consistent with the autocatalytic reaction model.The reaction activation energy of p-TTPES are 165.70,167.54 and 165.94 kJ/mol obtained by means of Kissinger,Ozawa,Flyn-Wall-Ozawa kinetic analysis methods and non-isothermal DSC curves,respectively,and the corresponding pre-exponential factor(A)was 2.76×10^(13) s^(-1).The 5%thermogravimetric temperature(T_(d5))in resin nitrogen is beyond 460℃,and the residue carbon rate of the resin is 74%at 800℃.Combined with DSC and TG analysis,it is found that when the carbon atoms number of aromatic monomer substituent is similar or the same,the structure change has little influence on the activation energy of monomer reaction,but has a great influence on the thermal stability of resin.

关 键 词：Grignard反应 对甲苯基三苯乙炔基硅烷 等温DSC法 非等温DSC法 自催化模型 

分 类 号：V255[一般工业技术—材料科学与工程]