微量热法研究GAP与BPS固化反应  

Study on Curing Reaction of GAP and BPS by Microcalorimetry

作　　者：肖立柏[1] 任晓宁[1] 高红旭[1] 赵凤起[1] 李娜[1] 付青山 赵昱[1] XIAO Li-bai;REN Xiao-ning;GAO Hong-xu;ZHAO Feng-qi;LI Na;FU Qing-shan;ZHAO Yu(Science and Technology on Combustion and Explosion Laboratory, Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

机构地区：[1]西安近代化学研究所燃烧与爆炸技术重点实验室,陕西西安710065

出　　处：《火炸药学报》2021年第1期50-54,共5页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21573173);国防科工局专项资助。

摘　　要：为了解叠氮黏合剂/非异氰酸酯固化体系的反应动力学和固化终点,通过非等温与等温微量热法,利用Kissinger方程和Crane方程研究了聚叠氮缩水甘油醚(GAP)与非异氰酸酯固化剂-丁二酸二丙炔醇酯(BPS)黏结体系的固化过程。结果表明,—C≡C—与—N_(3)摩尔比为1时,GAP/BPS黏结体系固化反应放热量最大;固化反应的表观活化能为80.33kJ/mol,指前因子为10^(8.42)s^(-1),反应级数为0.94,固化反应热为-1357.69J/g;拟合计算出了黏结体系的特征温度,凝胶温度为313.87K,固化温度为316.18K,后固化温度为338.55K;GAP/BPS黏结体系固化反应中存在自催化现象;拟合出黏结体系完全固化时间与温度之间的函数关系为y=4.13×10^(10)e^(-0.06441x)+5.029。In order to understand the reaction kinetics and end point of curing of azide binder/non-isocyanate bonding system,the curing behaviors of glycidyl azide polymer/bis-propargyl-succinate(GAP/BPS)bonding system were investigated by using non-isothermal and isothermal microcalorimetry according to Kissinger and Crane equations.The results show that the curing reaction has the maximum heat release when the molar ratio of—C≡C—and—N3 is 1.The apparent activation energy,pre-exponential factor,reaction order and curing reaction heat for the curing reaction of GAP/BPS bonding system are 80.33kJ/mol,10^(8.42)s^(-1),0.94 and-1357.69J/g,respectively.The characteristic temperatures of curing reaction system are calculated by curve fitting,and the values of gelation temperature,curing temperature and post-curing temperature are 313.87,316.18 and 338.55K,respectively.Autocatalytic phenomenon exists in the curing reaction process of the GAP/BPS bonding system.The function relation between the curing time and the curing temperature is also fitted with y=4.13×10^(10)e^(-0.06441x)+5.029.

关 键 词：物理化学 非异氰酸酯 BPS 聚叠氮缩水甘油醚 GAP 固化反应动力学 微量热 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]