[1]杨俊清①,王桂香①,高贫②,等.1, 3-二叠氮乙酰氧基-2, 2-二叠氮甲基丙烷（PEAA）的结构、性能与热分解机理的理论研究[J].爆破器材,2013,42(06):7-13.[doi:10.3969/j.issn.1001-8352.2013.06.002]
　YANG Junqing,WANG Guixiang,GAO Pin,et al.Theoretical Study on the Structure, Properties, and Thermal Decomposition Mechanism of the Azido Compound 1,3-di(azidoacetoxy)-2,2-di(azidomethyl)Propane (PEAA)[J].EXPLOSIVE MATERIALS,2013,42(06):7-13.[doi:10.3969/j.issn.1001-8352.2013.06.002]
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1, 3-二叠氮乙酰氧基-2, 2-二叠氮甲基丙烷（PEAA）的结构、性能与热分解机理的理论研究()
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《爆破器材》[ISSN:1001-8352/CN:32-1163/TJ]

卷:
42
期数:
2013年06
页码:
7-13
栏目:
基础理论
出版日期:
2013-12-20

文章信息/Info

Title:
Theoretical Study on the Structure, Properties, and Thermal Decomposition Mechanism of the Azido Compound 1,3-di(azidoacetoxy)-2,2-di(azidomethyl)Propane (PEAA)
文章编号:
4657
作者:
杨俊清①; 王桂香①; 高贫②; 贡雪东①
① 南京理工大学化工学院（江苏南京，210094)
②国家民用爆破器材质量监督检验中心（江苏南京，210094)
Author(s):
YANG Junqing①;  WANG Guixiang①;  GAO Pin②;  GONG Xuedong①
① School of Chemical Engineering, Nanjing University of Science and Technology (Jiangsu Nanjing, 210094)
②National Quality Supervision and Inspection Center for Industrial Explosive Materials (Jiangsu Nanjing, 210094)
关键词:
PEAA; 晶体结构; 爆轰性能; 热分解机理; 密度泛函理论
Keywords:
PEAA;  crystal structure;  detonation performance;  thermal decomposition mechanism;  density functional theory
分类号:
O641.12+1
DOI:
10.3969/j.issn.1001-8352.2013.06.002
文献标志码:
A
摘要:
1,3-二叠氮乙酰氧基-2,2-二叠氮甲基丙烷（PEAA）是一种玻璃态转化温度低而含氮量高的叠氮化物，具有作为含能增塑剂的潜在应用价值。文中采用密度泛函理论研究了其分子结构和红外光谱，预测了热力学函数、生成焓、爆轰性能和比冲；采用分子力学方法预测了其晶体结构和晶体密度；计算了多种可能的热解引发键的键解离能。结果表明，PEAA的热分解始于乙酰氧基上叠氮基的N=N键断裂，该过程经氢转移过渡态完成并放出氮气和热量，所需活化能约162 kJ/mol。与已有实际应用的叠氮增塑剂DATH（1,7-二叠氮基-2,4,6-三硝基-2,4,6-三氮杂庚烷）相比，PEAA的热稳定性更好。还考察了PEAA对硝胺改性双基推进剂能量性能的影响，发现无论用PEAA替代其中的NG还是RDX均使体系的能量输出和比冲增大，但体系的爆速和爆压略有降低。
Abstract:
1,3-di(azidoacetoxy)-2,2-di(azidomethyl)propane (PEAA) is an azido compound with a low glass transition temperature and a high nitrogen content. It has a great potential as the candidate of energetic plasticizers. In this paper, the molecular structure, infrared spectrum, thermodynamic functions, enthalpy of formation, detonation perfor mance, and specific impulse of PEAA were studied using the density functional theory. The crystal structure and crystal density were predicted using the molecular mechanics method. The bond dissociation energies of several possible thermal trigger bonds were calculated. Results show that the thermal decomposition of PEAA starts from the rupture of the N =N bond in the azidoacetoxy group. The process is completed synergistically via the transfer of H to the —N3 group to eliminate N2. The required activation energy is about 162 kJ/mol. PEAA has a better thermal stability than DATH (1,7-diazido-2,4,6-trinitro-2,4,6-triazaheptane), an azido plasticizer with practical applications. The influence of PEAA on the perfor mance of the nitramine modified doublebase propellants has been studied. Results show that replacing NG or RDX with PEAA slightly decreases the detonation velocity and detonation pressure, while increases the output energy and specific impulse of the propellants.

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备注/Memo

备注/Memo:
收稿日期：2013-06-18
基金项目：高等学校博士点新教师基金项目（20103219120014），江苏省自然科学基金（BK20130755），南京理工大学“卓越计划、紫金之星”基金项目
作者简介：杨俊清（1988~），女，硕士研究生，主要从事有机含能化合物的理论研究。
通信作者：高    贫（1969~），女，副研究员，主要从事含能物质理化分析和理论研究。
                    贡雪东（1967~），男，教授,主要从事含能材料的理论计算研究。
更新日期/Last Update: 2014-01-03