非等温DSC法研究聚丁二烯点击化学固化动力学  

Study on the Click Chemical Curing Reaction Kinetics of Polybutadiene Triazole System by Non-isothermal DSC Method

作　　者：王芮 李晓萌[1] 王晓青[1] 罗运军[1] WANG Rui;LI Xiao-meng;WANG Xiao-qing;LUO Yun-jun(School of Materials Science,Beijing Institute of Technology,Beijing 100081,China)

机构地区：[1]北京理工大学材料学院

出　　处：《火炸药学报》2019年第4期328-334,共7页Chinese Journal of Explosives & Propellants

摘　　要：为了更好地将聚丁二烯点击化学固化体系应用到实际工艺中,采用非等温差示扫描量热(DSC)法研究了端炔基聚丁二烯(PTPB)-三叠氮乙酸酯基丙烷(TAP)-端叠氮基聚乙二醇(APEG)体系的固化反应动力学;利用升温速率-温度外推法、Kissinger模型、Ozawa模型和Crane模型计算得到该固化体系的固化温度和动力学参数;通过n级固化动力学模型和非模型动力学(MFK)两种计算方法预测了该固化体系的等温固化行为。结果表明,若不添加催化剂,该体系60℃下固化反应活性低,固化速率非常缓慢,反应速率常数仅为3.13×10^-5min^-1;当添加催化剂CuCl的质量分数为0.1%时,其反应速率常数为5.6×10^-3min^-1,比端羟基聚丁二烯-甲苯二异氰酸酯(HTPB-TDI)固化体系高两个数量级;MFK预测结果与实测结果更为接近。此外,CuCl质量分数为0.1%时,该固化体系在30℃下完成固化仅需10.4h。In order to apply the click chemical curing system of polybutadiene into the practical process, the non-isothermal differential scanning calorimetry (DSC) method was used to investigate curing reaction kinetics of terminal alkynyl polybutadiene (PTPB)-triazide acetate propane (TAP)-terminal azido polyethylene glycol (APEG) system.The curing temperature and kinetic parameters of this curing system were calculated by the heating rate-temperature extrapolation method, the Kissinger model, the Ozawa model and the Crane model, respectively.The isothermal curing behavior of the curing system was predicted by n th order kinetics model and model free kinetics (MFK).The results indicate that this system has a low curing activity at 60℃ and the curing rate constant is only 3.13×10 ^-5 min^-1 .When the mass fraction of the catalyst (CuCl) is 0.1%, the rate constant is 5.6×10^-3 min^-1, which is two orders of magnitude higher than that of the hydroxyl terminated polybutadiene-toluene diisocyanate (HTPB-TDI) curing system.The MFK prediction result is closer to the measured result.In addition, when the mass fraction of CuCl is 0.1%, the curing system requires only 10.4h to complete curing at 30℃.

关 键 词：物理化学 高分子化学 固化动力学 非等温DSC 聚丁二烯 点击化学反应 

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]