摘要
基于密度泛函理论中的GGA/PBE和B3LYP方法,对高氯酸铵(AP)分解的质子转移过程及其分解产物引起的硝酸酯增塑聚醚(NEPE)推进剂固化体系PEG-TDI的氧化交联过程进行了分子模拟分析,以理清AP分解初始反应和NEPE推进剂中氧化交联反应机理。结果表明,分子结构和键离解能(BDE)计算结果显示,H4原子的转移是AP初始和再次质子转移过程的主要发生点;AP分解产物引起的PT氧化交联过程可划分为三个阶段:NO 2分子引起的H原子夺取反应、O原子引起的氧化反应、交联反应;H原子夺取反应为NO 2分子夺取PT分子的α—H、β—H,生成P1(—C·)和P2(—N·)两种带正电荷基团;氧化反应为O原子分别与P1和P2基团发生反应,生成P3(—C—O·)和P4(—N—O·)两种带负电荷基团;交联反应是在H原子夺取反应和氧化反应基础上发生的,最终生成—C—O—C—、—C—O—N—以及—N—O—N—三种结构链。
The proton transfer process of ammonium perchlorate(AP)and the oxygenizing and cross-linking process of PEG-TDI which is the curing system of nitrate ester plasticized polyether propellant were molecular simulated.Based on GGA/PBE and B3LYP methods in density functional theory to clarify the initial decomposition reaction of AP and the oxidative crosslinking reaction mechanism in NEPE propellant.The molecular structure and bond dissociation energy(BDE)calculation results show that that the transfer of H4 is the object of the initial and secondary proton transfer processes of AP.The oxygenizing and cross-linking process of PT,caused by AP decomposition,contains three stages:the hydrogen atom abstraction reaction caused by NO 2,oxidizing reaction caused by O atom and cross-linking reaction.Theα—H andβ—H of PT molecules are seized by NO 2 to generate two positively charged groups P1(—C·)and P2(—N·).In the oxidizing reaction,O atom reacts with the P1 and P2 groups respectively to generate two negatively charged groups P3(—C—O·)and P4(—N—O·).The cross-linking reaction,which occurs based on hydrogen abstraction and oxidizing reactions,contains three kinds of product forms,—C—O—C—,—C—O—N—and—N—O—N—.
作者
孔令泽
董可海
裴立冠
陈思彤
夏成
KONG Lingze;DONG Kehai;PEI Liguan;CHEN Sitong;XIA Cheng(College of Coast Defense Arm,Naval Aeronautical University,Yantai 264001,China;91550 Troops of PLA,Dalian 116023,China)
出处
《固体火箭技术》
EI
CAS
CSCD
北大核心
2020年第4期432-438,共7页
Journal of Solid Rocket Technology
基金
武器装备预先研究项目基金(51328050101)。
关键词
高氯酸铵(AP)
质子转移
H原子夺取反应
氧化交联
ammonium perchlorate(AP)
proton transfer
hydrogen atom abstraction reaction
oxygenizing and cross-linking
