含硼高能化合物的结构与性能理论研究
发布时间：2018-08-15 12:10
【摘要】：高能钝感是含能材料的发展方向,也是武器能源领域关注的热点问题。长期以来,人们改进含能材料的技术途径有两大类:一是寻找和合成新的化合物;二是在配方中加入相容性好的高能组分来提高含能材料的能量,同时,通过添加粘结剂、钝感剂来获得感度相对较低的混合药剂配方。无论采取何种途径获得新型高能化合物,其设计和合成都是根本所在,相关研究具有重要的理论意义和应用价值。硼由于具有高的燃烧热值,受到了人们的关注,但硼的反应需要外界供氧,而且此种材料的表面氧化膜在燃爆过程中有较强的阻碍作用,影响了其能量的释放。基于此问题,本文以设计兼具高热值、反应迅速、安全性好的含硼高能化合物为目标,利用密度泛函理论对硝基硼烷化合物的几何结构、成键特征、热力学稳定性以及光谱性质等进行理论研究。从理论上设计探索新型高能、钝感化合物,为新型高能钝感含能材料的研究提供理论支撑。论文主要研究内容如下:1在密度泛函理论在B3LYP/6-31+G~*水平上,对硼氧基取代TNT苯环上氢原子所得化合物进行几何结构、热力学性质以及其前线轨道能级差ΔE_(gap)和Wiberg键级进行了理论研究;2在密度泛函理论在B3LYP/6-31+G~*水平上,对TNA的硼氧基取代衍生物的几何结构、热力学性质以及其前线轨道能级差ΔE_(gap)和Wiberg键级进行了理论研究;3采用密度泛函理论在B3LYP/6-31+G~*水平上,对TNP硼氧基取代物的键长,红外光谱振动,热力学性质以及前线轨道能级差ΔE_(gap)和wiberg键级进行理论研究;4采用密度泛函理论在B3LYP/6-31+G~*水平上,用原子化反应法对硼氢化合物B_2H_6硝基衍生物的稳定性、生成焓和爆热等参数进行了理论计算;5采用密度泛函理论在B3LYP/6-31+G~*水平上,对硼氢化合物B_4H_2硝基衍生物的稳定性、生成焓和爆热等参数进行了理论计算;6采用密度泛函理论在B3LYP/6-31+G~*水平上,对硼氢化合物B_5H_9硝基衍生物的稳定性、生成焓和爆热等参数进行了理论计算。理论计算结果表明:1 TNT硼氧基衍生物中硼氧键为三键,C-BO键的键级为0.86,C-NO_2键的键级为0.90,C-BO键的键级相对最弱,可能是标题物的热解或起爆引发键;通过自然轨道分析得出TNT-(BO)_2前线轨道能级差值ΔE_(gap)大于TNT-BO,这表明TNT硼氧基衍生物稳定性随取代基数的增加而增强;通过爆热计算得知TNT硼氧基衍生物的爆热明显大于TNT,由此可推断,TNT硼氧基衍生物是一种潜在的高爆热钝感含能材料;2 TNA硼氧衍生物中硼氧键是典型三键;通过自然轨道分析在TNA硼氧衍生物中N-H键最弱,可能是标题物的热解或起爆引发键;并且随着取代基数目的增加,前线轨道能级差ΔE_(gap)增大,表明化合物稳定性增强;通过爆热计算得知TNA硼氧基衍生物的爆热大于TNA,由此可推断,TNA硼氧基衍生物是一种潜在的高爆热钝感含能材料;3 TNP硼氧衍生物中硼氧键是典型三键;通过自然轨道分析可知,随着取代基数目的增加,TNP硼氧衍生物的前线轨道能级差ΔE_(gap)增大,表明化合物的稳定性随取代基数目的增加而增大;TNP硼氧基衍生物的爆热比TNP爆热大,而且计算表明硼氧基取代苯环上氢原子后会使得化合物更加稳定,由此可推断,TNP硼氧基衍生物是一种潜在的高爆热钝感含能材料;4采用密度泛函理论研究结果表明,B_2H_6硝基衍生物的爆压、爆速随着硝基数的增加也在增加;自然轨道分析得知B2H2(NO_2)4化合物的ΔE_(gap)值为459.27 k J/mol,接近于TNT、TNA和TNP的硼氧基衍生物的ΔE_(gap)值,说明在B_2H_6中即使硝基数增加到4个时,所得到的硝基硼烷也是相当稳定的,可以作为潜在的新型高能钝感含能材料使用;5采用密度泛函理论对B_4H_2硝基衍生物和TNT进行了研究比较,研究结果表明,标题物的理论密度、爆速和爆压略低,但是爆热比TNT大很多;自然轨道分析得知B4HNO_2和B4(NO_2)_2没有B_4H_2稳定,即B4HNO_2和B4(NO_2)_2的感度较大,在使用前可能需要经过降感处理;6通过自然轨道分析了B_5H_9硝基衍生物的ΔE_(gap)值,发现其与TNT轨道能级差ΔE_(gap)值相近,可以认为这些化合物稳定性与TNT稳定性相近;化合物中B-NO_2键相对较弱,可能是标题物的热解或起爆引发键;化合物中随着硝基数的增加,化合物的爆速和爆压都在增大,最大爆速为6.98 km/s,最大爆压为19.87 Gpa,虽然比TNT低,但是最大爆热为1946.52 J/g,远大于TNT的爆热(1425.94 J/g)。
[Abstract]:High-energy insensitivity is the development direction of energetic materials and a hot issue in the field of weapon energy. For a long time, there are two ways to improve energetic materials: one is to find and synthesize new compounds; the other is to add compatible high-energy components into the formula to improve the energy of energetic materials, and at the same time, to add bonding. Designing and synthesizing new high-energy compounds by any means is fundamental. Relevant research has important theoretical significance and application value. Boron has attracted people's attention because of its high combustion calorific value, but the reaction of boron requires external oxygen supply. Based on this problem, in order to design boron-containing high-energy compounds with high calorific value, rapid reaction and good safety, the geometric structure, bonding characteristics and thermodynamics of nitroborane compounds were studied by density functional theory. Theoretical studies on stability and spectral properties have been carried out. New energetic and insensitive compounds have been designed and explored theoretically to provide theoretical support for the study of new energetic and insensitive energetic materials. The geometric structure, thermodynamic properties and frontier orbital energy difference E_ (gap) and Wiberg bond level of TNA were studied theoretically. 3 The bond length, infrared spectroscopy, thermodynamic properties and frontier orbital energy difference E_ (gap) and Wiberg bond level of TNP boroxy substitutes were studied theoretically at B3LYP/6-31+G~* level by density functional theory. 4 The derivatization of borohydride B_2H_6 by atomization reaction at B3LYP/6-31+G~* level was studied by density functional theory. The stability, enthalpy of formation and detonation heat of borohydride B_4H_2 nitro-derivatives were calculated theoretically at B3LYP/6-31+G~* level by using density functional theory. The stability, enthalpy of formation and detonation heat of borohydride B_4H_2 nitro-derivatives were calculated theoretically. The density functional theory was used to calculate the B_5H_9 nitro-compounds at B3LYP/6-31+G~* level. The stability, enthalpy of formation and heat of detonation of the derivatives were calculated theoretically. The results show that: 1. The boron-oxygen bond of TNT boron-oxygen derivatives is triple bond, the bond order of C-BO bond is 0.86, the bond order of C-NO_2 bond is 0.90, and the bond order of C-BO is relatively weak, which may be the title compound's pyrolysis or initiation bond. TNT - (BO) _2 frontline orbital energy level difference_E_ (gap) is greater than TNT-BO, which indicates that the stability of TNT boroxy derivatives increases with the number of substituents; the detonation heat of TNT boroxy derivatives is obviously higher than that of TNT by thermal calculation, which can be inferred that TNT boroxy derivatives are potential energetic materials with high thermal insensitivity; Boron-oxygen bond in TNA boron-oxygen derivatives is a typical triple bond; the N-H bond is the weakest in TNA boron-oxygen derivatives by natural orbital analysis, which may be the pyrolysis or initiation bond of the title compounds; and with the number of substituents increasing, the frontier orbital energy gap E_ (gap) increases, indicating that the stability of the compounds is enhanced; the detonation heat of TNA boron-oxygen derivatives is calculated by detonation heat calculation. When the number of substituents increased, the frontier orbital energy difference_E_ (gap) of TNP boron-oxygen derivatives increased, indicating that the stability of TNP boron-oxygen derivatives increased with substitution. The detonation heat of TNP boroxy derivatives is larger than that of TNP, and calculation shows that substituting hydrogen atoms on benzene ring with boroxy groups makes the compounds more stable. It can be inferred that TNP boroxy derivatives are potential energetic materials with high detonation heat insensitivity. The detonation pressure and the detonation velocity of the derivatives also increase with the increase of the number of nitro groups; the natural orbital analysis shows that the E_ (gap) value of B2H2 (NO_2)4 compound is 459.27 K J/mol, which is close to the E_ (gap) value of boroxy derivatives of TNT, TNA and TNP, indicating that the nitroborane obtained in B_2H_6 is quite stable even if the number of nitro groups increases to 4. The results show that the theoretical density, detonation velocity and pressure of the title compound are slightly lower, but the detonation heat is much larger than that of TNT. The natural orbital analysis shows that B4HNO_2 and B4 (NO_2)_2 are not stable, that is, B4HNO_2 is not stable. The sensitivity of B4(NO_2)_2 is higher than that of B4(NO_2)_2, which may need to be reduced before use. 6 The E_ (gap) value of B_5H_9 nitro derivatives is analyzed by natural orbital method, and it is found that the stability of these compounds is close to that of TNT, and the B-NO_2 bond is relatively weak, which may be the title compound. The detonation velocity and pressure of the compounds increase with the increase of nitro number, the maximum detonation velocity is 6.98 km/s, the maximum detonation pressure is 19.87 Gpa, although lower than TNT, the maximum detonation heat is 1946.52 J/g, which is much higher than that of TNT (1425.94 J/g).
【学位授予单位】：中北大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ560.1
[Abstract]:High-energy insensitivity is the development direction of energetic materials and a hot issue in the field of weapon energy. For a long time, there are two ways to improve energetic materials: one is to find and synthesize new compounds; the other is to add compatible high-energy components into the formula to improve the energy of energetic materials, and at the same time, to add bonding. Designing and synthesizing new high-energy compounds by any means is fundamental. Relevant research has important theoretical significance and application value. Boron has attracted people's attention because of its high combustion calorific value, but the reaction of boron requires external oxygen supply. Based on this problem, in order to design boron-containing high-energy compounds with high calorific value, rapid reaction and good safety, the geometric structure, bonding characteristics and thermodynamics of nitroborane compounds were studied by density functional theory. Theoretical studies on stability and spectral properties have been carried out. New energetic and insensitive compounds have been designed and explored theoretically to provide theoretical support for the study of new energetic and insensitive energetic materials. The geometric structure, thermodynamic properties and frontier orbital energy difference E_ (gap) and Wiberg bond level of TNA were studied theoretically. 3 The bond length, infrared spectroscopy, thermodynamic properties and frontier orbital energy difference E_ (gap) and Wiberg bond level of TNP boroxy substitutes were studied theoretically at B3LYP/6-31+G~* level by density functional theory. 4 The derivatization of borohydride B_2H_6 by atomization reaction at B3LYP/6-31+G~* level was studied by density functional theory. The stability, enthalpy of formation and detonation heat of borohydride B_4H_2 nitro-derivatives were calculated theoretically at B3LYP/6-31+G~* level by using density functional theory. The stability, enthalpy of formation and detonation heat of borohydride B_4H_2 nitro-derivatives were calculated theoretically. The density functional theory was used to calculate the B_5H_9 nitro-compounds at B3LYP/6-31+G~* level. The stability, enthalpy of formation and heat of detonation of the derivatives were calculated theoretically. The results show that: 1. The boron-oxygen bond of TNT boron-oxygen derivatives is triple bond, the bond order of C-BO bond is 0.86, the bond order of C-NO_2 bond is 0.90, and the bond order of C-BO is relatively weak, which may be the title compound's pyrolysis or initiation bond. TNT - (BO) _2 frontline orbital energy level difference_E_ (gap) is greater than TNT-BO, which indicates that the stability of TNT boroxy derivatives increases with the number of substituents; the detonation heat of TNT boroxy derivatives is obviously higher than that of TNT by thermal calculation, which can be inferred that TNT boroxy derivatives are potential energetic materials with high thermal insensitivity; Boron-oxygen bond in TNA boron-oxygen derivatives is a typical triple bond; the N-H bond is the weakest in TNA boron-oxygen derivatives by natural orbital analysis, which may be the pyrolysis or initiation bond of the title compounds; and with the number of substituents increasing, the frontier orbital energy gap E_ (gap) increases, indicating that the stability of the compounds is enhanced; the detonation heat of TNA boron-oxygen derivatives is calculated by detonation heat calculation. When the number of substituents increased, the frontier orbital energy difference_E_ (gap) of TNP boron-oxygen derivatives increased, indicating that the stability of TNP boron-oxygen derivatives increased with substitution. The detonation heat of TNP boroxy derivatives is larger than that of TNP, and calculation shows that substituting hydrogen atoms on benzene ring with boroxy groups makes the compounds more stable. It can be inferred that TNP boroxy derivatives are potential energetic materials with high detonation heat insensitivity. The detonation pressure and the detonation velocity of the derivatives also increase with the increase of the number of nitro groups; the natural orbital analysis shows that the E_ (gap) value of B2H2 (NO_2)4 compound is 459.27 K J/mol, which is close to the E_ (gap) value of boroxy derivatives of TNT, TNA and TNP, indicating that the nitroborane obtained in B_2H_6 is quite stable even if the number of nitro groups increases to 4. The results show that the theoretical density, detonation velocity and pressure of the title compound are slightly lower, but the detonation heat is much larger than that of TNT. The natural orbital analysis shows that B4HNO_2 and B4 (NO_2)_2 are not stable, that is, B4HNO_2 is not stable. The sensitivity of B4(NO_2)_2 is higher than that of B4(NO_2)_2, which may need to be reduced before use. 6 The E_ (gap) value of B_5H_9 nitro derivatives is analyzed by natural orbital method, and it is found that the stability of these compounds is close to that of TNT, and the B-NO_2 bond is relatively weak, which may be the title compound. The detonation velocity and pressure of the compounds increase with the increase of nitro number, the maximum detonation velocity is 6.98 km/s, the maximum detonation pressure is 19.87 Gpa, although lower than TNT, the maximum detonation heat is 1946.52 J/g, which is much higher than that of TNT (1425.94 J/g).
【学位授予单位】：中北大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ560.1
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