NEPE推进剂中叠氮类黏合剂分子固化反应动力学模拟研究  

Simulation study on the curing reaction kinetics of azide adhesive molecules in NEPE propellant

作　　者：赵骁 张鑫 臧启光 杨二刚 周少魁 吴芳 ZHAO Xiao;ZHANG Xin;ZANG Qiguang;YANG Ergang;ZHOU Shaokui;WU Fang(National Key Laboratory of Aerospace Chemical Power,Xiangyang 441003,China;Hubei Institute of Aerospace Chemotechnology,Xiangyang 441003,China)

机构地区：[1]航天化学能源全国重点实验室,襄阳441003 [2]湖北航天化学技术研究所,襄阳441003

出　　处：《固体火箭技术》2025年第1期85-92,共8页Journal of Solid Rocket Technology

摘　　要：叠氮类黏合剂分子的固化反应动力学模型是了解相应硝酸酯增塑聚醚(NEPE)推进剂交联网络形成机理的重要途径。采用密度泛函理论(DFT)及过渡态理论(TST)方法,研究了缩水甘油叠氮聚醚(GAP)、3,3-双叠氮甲基氧杂环丁烷-四氢呋喃共聚醚(PBT)及三羟甲基丙烷(TMP)、硝化甘油(NG)、奥克托今(HMX)的分子结构、电子结构、分子间相互作用,以及分别在甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)体系中的固化反应动力学。结果表明,PBT的极性及稳定性均高于GAP,作为氢键供体的羟基与叠氮拥有更强的电负性。基于不同体系反应活化能垒ΔG和反应速率常数k的计算结果,TDI体系中黏合剂分子的固化反应速度(2.68×10^(-34)cm^(3)·mol^(-1)·s^(-1))显著高于HDI固化体系(3.50×10^(-35)cm^(3)·mol^(-1)·s^(-1))。同时,TMP与不同叠氮类黏合剂分子均能形成较强的分子间相互作用,并能够显著提高固化反应速率。此外,TDI体系中强氢键对固化反应的促进作用在高温下仍表现明显。The exploration of curing reaction kinetic models on various azide adhesive molecules is an important pathway for understanding the formation mechanism of cross-linked network in corresponding solid propellant formula.The molecular structure,electronic structure and intermolecular interaction of glycidol azide polyether(GAP),3,3-bis(azidomethyl)oxetane-tetrahydrofuran copolyether(PBT),trimethylolpropane(TMP),nitroglycerin(NG)and octogen(HMX)were studied by density functional theory(DFT)and transition state theory(TST).The curing reaction kinetics of GAP,PBT,TMP,NG and HMX in toluene diisocyanate(TDI)and hexamethylene diisocyanate(HDI)systems were also studied.The results show that the polarity and stability of PBT are higher than that of GAP,and the hydroxyl group and azide as hydrogen bond donors possess stronger electronegativity.Based on the calculation results of activation energy barrierΔG and reaction rate constant k of different systems,the curing reaction rate constant of adhesive molecules in TDI system(2.68×10^(-34)cm^(3)·mol^(-1)·s^(-1))is significantly higher than that in HDI system(3.50×10^(-35)cm^(3)·mol^(-1)·s^(-1)).TMP can form strong intermolecular interactions with different adhesive molecules,which significantly promote the curing reaction rate of the corresponding azide adhesive systems.In addition,the facilitation of strong hydrogen bonds on the curing reaction in the TDI system is obvious at high temperatures.

关 键 词：固体推进剂 叠氮黏合剂 固化反应动力学 密度泛函理论 分子间相互作用 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]