HTPB/TDI粘结体系的固化反应动力学

为了解决工程应用中遇到的固化终点问题,采用等温与非等温差示扫描量热法(DSC法),通过模拟n级反应动力学模型,并根据Kissinger法、Crane法研究了高聚物粘结炸药(PBX)用端羟基聚丁二烯(HTPB)型粘结体系的固化反应动力学。结果表明,HTPB/TDI粘结体系固化反应的表观活化能为54.61kJ·mol~(-1),反应级数为0.87,指前因子为192.80s~(-1),固化反应热Hu为482.87J·g~(-1)。该体系的固化反应过程中存在自催化现象。加入二月桂酸二丁基锡(T12)催化剂后,粘结体系的固化反应速率增大、反应温度降低。拟合出了固化温度与固化时间之间的函数关系,当固化温度取60℃时,求得固化时间约为3.91天,与实际工程应用中的4~6天相符。

Curing Reaction Kinetics of HTPB/TDI Bonding System

To solve the problem on end point of curing encountered in engineering application,the curing reaction kinetics of hydroxyl-terminated polybutadiene(HTPB)type bonding system used for polymer bonded explosive(PBX)wss studied by isothermal and non-isothermal differential scanning calorimetry(DSC)through the simulation of n-order reaction kinetic model according to Kissinger method and Crane method.Results show that the apparent activation energy,reaction order,pre-exponential factor and curing reaction heat for curing reaction of HTPB/TDI bonding system are 54.61 kJ·mol-1,0.87,192.80 s-1 and 482.87 J·g-1,respectively.Autocatalytic phenomenon exists in the curing reaction process of the system.After adding the dibutytin dilaureate(T12)catalyst,the curing reaction rate of the bonding system increases and the reaction temperature decreases.The function relation between the curing temperature and the curing time is fitted and obtained.Calculated curing time is about 3.91 days when the curing temperature is 60℃,which is consistent with 4-6 days in the practical engineering applications.