有机笼状高能量密度材料（HEDM）的分子设计和配方设计初探
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摘要
运用理论和计算化学方法,主要是量子力学(QM)、分子力学(MM)和分子动力学(MD)等方法,对两类重要有机笼状化合物金刚烷和六氮杂金刚烷(HAA)的多系列高能衍生物以及著名的高能量密度化合物(HEDC)六硝基六氮杂异伍兹烷(CL-20)的结构和性能,进行了较为系统的计算、模拟和研究。从气相分子、固态晶体至复合材料(高聚物黏结炸药PBX),完成了寻求高能量密度材料(HEDM)的全过程研究。全文大体包括三部分内容:
第一部分是HEDC的“分子设计”。基于量子化学计算首次建议和运用判别HEDC的定量标准(密度ρ>1.9g·cm~(-3),爆速D>9.0km·s~(-1)和爆压p>40.0GPa),并兼顾其稳定性(热解引发键离解能BDE>120kJ·mol~(-1))要求,从上述多系列有机笼状化合物中推荐了7种HEDC。
首先,以量子化学第一性原理DFT-B3LY/6-31G*水平的全优化构型,求得系列多硝基金刚烷(PNA)的红外光谱(IR)和298~800K温度范围的热力学性质(C_(p,m)°、S_m°和H_m°);设计等键反应求得其气相生成热(HOF);按0.001e·Bohr-3电子密度曲面所包含的体积求得晶体理论密度(ρ);按Kamlet-Jacobs方程估算它们的爆速(D)和爆压(p)。运用UHF-PM3方法求得该系列化合物的各可能引发键的均裂活化能(E_a),预测其热解引发机理和稳定性相对大小;在B3LYP/6-31G*水平求得引发键C–NO_2键离解能(EC–N);发现热解引发键的键级(B_(C–NO2))、E_(C–N)、E_a以及–NO_2上净电荷(QNO_2)对判别稳定性或感度的等价线性关系。按照我们建议的HEDC的定量标准和稳定性要求,发现1,2,3,4,5,6,7,8-八硝基金刚烷、1,2,3,4,5,6,7,8,9-九硝基金刚烷和1,2,3,4,5,6,7,8,9,10-十硝基金刚烷三种化合物是值得推荐的潜在HEDC,从而否定了国外前人由基团加和法得出的十一硝基金刚烷是PNA系列最佳HEDC目标物的结论。此外,还对金刚烷的硝酸酯基系列化合物作类似的理论研究,根据判别HEDC的能量与稳定性相结合的定量标准,发现1,2,4,6,8,9,10-七硝酸酯基金刚烷可作为HEDC目标物。
其次,在B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G*水平下,对NO_2气相硝化金刚烷的反应机理进行动态理论计算。求得各可能反应途径的过渡态,通过比较各可能反应途径所需反应势垒(E_a),确定了该反应的最佳途径,所得结论与实验相符,表明理论计算对指导HEDC的实验合成有助。
再次,与研究多硝基金刚烷系列类似,在多硝基六氮杂金刚烷(PNHAA)系列衍生物结构-性能计算研究的基础上,报导了它们按等键反应设计所得生成热(HOF),估算了晶体理论密度(ρ)、爆热(Q)、爆速(D)和爆压(p);通过比较两种可能引发键(C–N和N–NO_2)的键离解能(E_(C–N)和E_(N–NO2)),揭示其热解机理,确定引发键为N–NO_2键;将稳定性或感度与多种理论结构参数进行了关联。类似地,按HEDC的ρ、D、p定量标准和引发键离解能(EN–N)大小,求得含四硝基、五硝基尤其是六硝基六氮杂金刚烷三种化合物为潜在HEDC。
最后,作为PNHAA研究的扩展,对HAA其它三类(即–CN、–NC和–ONO_2基)衍生物进行结构和性能研究,为新型HEDM的分子设计增添了信息和规律。计算结果表明,HAA的–CN和–NC衍生物虽然生成热大、爆热高,但因负氧平衡,其ρ、D和p较低,故不是HEDC。(据此可推测在金刚烷的该两类衍生物中也不可能找到HEDC。) 2,4,6,8-、2,4,6,9-、2,4,6,8,10-和2,4,6,8,9,10-多硝酸酯基HAA虽满足HEDC的ρ、D、p定量标准,但引发键O–NO_2键离解能(EO–N)太小,表明其稳定性极差(如2,4,6,8-四硝酸酯基HAA的EO–N仅为29.81 kJ?mol-1),故它们亦不宜推荐为实用HEDC。
第二部分包括分子堆积方式预测和晶体结构与性能的理论研究。对前述由分子设计求得的七种HEDC进行空间堆积方式预测,并对求得的合理晶型作周期性计算,报导其能带结构和性能。对已获得实用的当前最重要的HEDC—CL-20的四种晶型进行周期性从头计算,并研究了压强对其中最稳定晶型ε-CL-20的影响。
首先,借助MS程序中Polymorph模块,在7种最可几空间群(P21/c、P-1、P212121、P21、C2/c、Pbca和Pna21)中,运用分子力学(MM),对已有实验晶型的ε-CL-20和前面找到的七种潜在HEDC进行最佳分子堆积方式搜索,分别地预测出它们的合理晶型。运用DFT-GGA-RPBE方法和Compass、Dreiding两种力场,求得它们各自的优化构型。经比较表明,Dreiding力场适用于硝基和硝酸酯类化合物,而Compass力场则较为适用于硝胺和硝酸酯类。综合两种力场的预测结果,求得ε-CL-20、2,4,6,8-四硝基六氮杂金刚烷、2,4,6,8,10-五硝基六氮杂金刚烷、2,4,6,8,9,10-六硝基六氮杂金刚烷和1,2,4,6,8,9,10-七硝酸酯金刚烷分别属于P21/c、P-1、P-1、P21/c和P21/c空间群;1,2,3,4,5,6,7,8-八硝基金刚烷、1,2,3,4,5,6,7,8,9-九硝基金刚烷和1,2,3,4,5,6,7,8,9,10-十硝基金刚烷则分别属于C2/c、P21/c和C2/c空间群。
其次,运用Dmol3程序包中DFT-GGA-RPBE方法,对ε-CL-20晶体和七种潜在HEDC的合理预测晶型进行周期性能带结构从头计算。ε-CL-20的预测晶型与实验晶体呈现类似的能带结构和态密度(DOS),表明所使用的方法可靠。考察各晶体的DOS注重分析Feimi能级附近导带和价带的组成,预示硝胺类即ε-CL-20和多硝基六氮杂金刚烷的热解引发键为N–NO_2,预示多硝基和多硝酸酯基金刚烷的热解引发键分别为C–NO_2和O–NO_2,这些均与实验或由气相分子理论计算导致的结论相一致。我们建议要特别关注2,4,6,8,9,10-六硝基六氮杂金刚烷。它的DOS与CL-20的DOS很相似;其带隙ΔEg与ε-CL-20的也接近,预示其感度与ε-CL-20相当,这与由分子中N–NO_2键离解能(E_(N–N))导致的结论相一致;但因其预测密度值(2.315g·cm-3)高于ε-CL-20的密度(2.173g·cm-3),故表明若能成功合成,则其能量性质将优于当前最热门的CL-20。
最后,对实际存在的CL-20的四种晶型(α·H_2O、β、γ和ε-CL-20)进行周期性能带结构从头计算,按带隙(ΔE_g)大小预测其感度排序ε<β<γ<α·H_2O,与实验事实相一致,符合最易跃迁原理(PET),给出了分子型晶体感度理论判别的首例。以最稳定晶型ε-CL-20为例,研究压强对其几何、电子结构和性能的影响。结果表明,由低压到高压,ε-CL-20晶体均呈现一定的各向异性特征;当压强小于10GPa时,晶胞参数、能带、ΔEg和DOS受压强影响较小;而当压强由10GPa增加到400GPa时,这些参数均发生较大变化;且当压强为400GPa时,带隙趋近于零,DOS呈平缓曲线,分子的N–NO_2二面角发生很大扭曲,表明ε-CL-20已具某些金属属性。
第三部分用分子动力学(MD)方法模拟研究了ε-CL-20基PBX亦即HEDM的结构和性能。考察了黏结剂种类、黏结剂含量(W%)、温度(T)和晶体缺陷等因素对四大基本属性(力学性能、能量性质、相容性和安全性)的影响,为实际配方设计提供信息、奠定基础。
首先,按“切割分面”模型,将四种氟聚物惰性黏结剂:聚偏二氟乙烯(PVDF)、聚三氟氯乙烯(PCTFE)、F2311和F2314分别置于ε-CL-20的3个不同晶面(001)、(010)和(100)上,对所得十二种PBX模型进行MD模拟。基于静态力学分析,求得它们的力学性能(弹性系数、拉伸模量、体模量、剪切模量和泊松比)。结果表明,加入少量氟聚物即能有效改善ε-CL-20的力学性能;因ε-CL-20的(001)面分子密度较大,与黏结剂相互作用较强,故其对力学性能的改善效应也较强;在四种黏结剂中,以F2314与ε-CL-20构成的PBX的综合力学性能较好;四种黏结剂对ε-CL-20的爆炸性质(爆热、爆速和爆压)影响较小,且彼此相差不大。
其次,选取上述较佳PBX模型ε-CL-20(001)/F2314为例,通过MD模拟,探讨了T、W%和晶体缺陷(空位和掺杂)对PBX性能的影响。结果表明,T对力学性能有一定影响,而对结合能(E_(bind))影响较小。随W%增加,F_(2314)与ε-CL-20分子间的总结合能(E_(bind))增加,但单根F_(2314)链对应的平均结合能(E_(aver))却降低;含4.69%F_(2314)的PBX具有较好的力学性能和爆轰性能,与实际配方中黏结剂含量(小于5%)相符。就我们所取两种ε-CL-20晶体缺陷模型而言,与“完美”晶体相比,空位缺陷及其相应PBX的力学性能(主要指拉伸模量、体模量和剪切模量)变化较大,而掺杂模型的结构和性能变化较小。
最后,选择三种不同类型的含能黏结剂[聚氨基甲酸乙酯(Estane)、聚叠氮甘油醚(GAP)和端羟基聚丁二烯(HTPB)]与ε-CL-20构成PBX进行MD模拟。首次把模拟所得黏结剂与主体炸药之间的结合能(E_(bind)),与它们之间的物理相容性进行关联,判别并解释了相容性实验结果。通过对相关函数g(r)分析,揭示了各黏结剂与ε-CL-20之间相互作用的方式。对于尚无实验结果的ε-CL-20/聚乙二醇(PEG)PBX进行类似的MD模拟,预测了它的相关性能。综合比较模拟所得多种PBX的力学、爆炸和安全性能,为优选黏结剂提供了信息和参考依据。
总之,本文基于量子化学发展了一套计算高能物质密度(ρ)、爆速(D)和爆压(p)的简便方法,建议了判别HEDC的能量(ρ、D、p)和稳定性(引发键BDE)相结合的定量标准,在多取代基金刚烷和六氮杂金刚烷多系列高能衍生物中,找到了七种HEDC潜在目标物。运用MM和QM相结合的方法,预测了这七种HEDC分子的空间排列方式和晶体能带结构,特别推荐合成性能将优于CL-20的六硝基六氮杂金刚烷。还以MD方法模拟研究了以CL-20为基的多种PBX(亦即HEDM)在不同温度、浓度以及晶体“完美”和“缺陷”条件下的结构和多种性能,为优选黏结剂、进行HEDM配方设计提供了信息和指导。这些工作在HEDM多学科交叉前沿研究领域中具有开拓创新性,圆满地完成了国防973和国家自然科学基金等项目赋予的各项任务。
The dissertation is devoted to systematic researches on the structures and properties of the two types of important organic cage compounds (a series of the high energy derivatives of adamantane and hexaazaadamantane) and the well-known high energy density compound (HEDC) hexanitrohexaazaisowurtzitane (CL-20), using the theoretical and computational chemistry methods, mainly including quantum mechanics (QM), molecular mechanics (MM), molecular dynamics (MD) and so on. We have completed the whole process of searching for high energy density materials (HEDM) from gas molecules to crystal structures, and then to complex materials (such as polymer bonded explosives, PBX). The dissertation is divided into three parts:
The first part concentrates on the“molecular design”of HEDC. Based on the QM calculations, both the quantitative standard (densityρ>1.9g·cm~(-3), detonation velocity D>9.0km·s~(-1), and detonation pressure p>40.0GPa.) as an HEDC and the stability requirement (the dissociation energy of trigger bond, BDE>120kJ·mol~(-1)) are first time suggested to screen out seven potential HEDC from the above referred organic cage compounds.
First, based on the fully optimized structures at the DFT-B3LYP/6-31G* level, the infrared (IR) spectra and thermodynamic properties (C_(p,m)°, S_m°, and H_m°) in the range of 298~800K are computed for polynitroadamantanes (PNA); their gas heats of formation (HOF) are obtained by designing isodesmic reactions; according to the volume inside a contour of 0.001e·Bohr~(-3), their theoretical crystal densities (ρ) are evaluated; and their D and p are estimated according to the Kamlet-Jacobs equations. The UHF-PM3 method is employed to evaluate the activation energy (Ea) for the homolysis of each possible trigger bond, and to predict the pyrolysis initiation mechanism and relative stability of PNA; the dissociation energy (E_(C–N)) of each trigger bond C–NO_2 is calculated at the B3LYP/6-31G* level; and it is found that all the bond order of the trigger bond (BC–N), EC–N, Ea, and the net charge on–NO_2 (QNO_2) can be equally used to predict the stability or sensitivity of PNA. According to the suggested quantitative standard and stability requirement as an HEDC, 1,2,3,4,5,6,7,8-octanitroadamantane, 1,2,3,4,5,6,7,8,9-nonanitr -oadamantane, and 1,2,3,4,5,6,7,8,9,10-decanitroadamantane are worth recommending as potential HEDC, and this denies the foreigners’conclusion from group additivity method that the PNA with 11 nitro groups was the target compound. Besides, similar studies are carried out on the–ONO_2 derivatives of adamantane; and in the light of the standard, 1,2,4,6,8,9,10-adamantylheptanitrate also is considered as an HEDC candidate.
Second, at the B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G* level, the reaction mechanism on the nitration of adamantane with NO_2 is investigated. All the transition states of each possible reaction path are found, and the most possible reaction path is confirmed by comparing each reaction barrier (Ea). The obtained conclusion agrees well with that from the experiment, presenting the availability of theoretical computation in guiding HEDC synthesis.
Third, in the same way, on the basis of the studies on the structures and properties of the polynitrohexaazaadamantanes (PNHAA), their HOF obtained by isodesmic reaction are reported; theirρ, D and p are evaluated; by comparing the dissociation energies (EC–N and EN–N) of two possible trigger bonds (C–N and N–NO_2), their thermolysis mechanisms is revealed, and the N–NO_2 bond is predicted as the trigger bond; their stability or sensitivity has been correlated with various theoretical structure parameters. Similarly, according to theρ, D and p criteria as an HEDC and the value of EN–N, three PNHAA with 4, 5 and 6–NO_2 are recommended as the potential HEDC.
Finally, as an extension of the studies on PNHAA, further studies on the structures and properties of the other three kinds of HAA derivatives (–CN,–NC, and–ONO_2) are made to provide more basis data for the molecular design of new type of HEDM. The calculation results indicate that although the–CN and–NC derivatives of HAA show high heats of formation and high heats of detonation, they cannot meet the criteria as an HEDC, due to their negative oxygen balances and lowerρ, D and p. (Accordingly, none of these two types of adamantane derivatives can be predicted as HEDC). 2,4,6,8-, 2,4,6,8,10-, and 2,4,6,8,9,10-hexaazaadamantylnitrates satisfy theρ, D, and p standard as an HEDC, their dissociation energies (EO–N) of trigger bond O–NO_2, however, are too small (for example, EO–N of 2,4,6,8-hexaazaadamantyltetranitrate is only 29.81 kJ.mol-1), thus they all cannot be recommended as practical HEDC, too.
The second part focuses on molecular packing predictions and theoretical studies on the structures and performance of crystals. The predictions of spacial packing are made for the seven HEDC obtained from the above molecular design; and the band structures and performances of the reasonably predicted crystals are calculated from periodic calculations. Periodic Ab inito calculations are also carried out on the four polymorphs of the currently most important HEDC–CL-20, and the influences of pressure on the most stableε-CL-20 crystal is investigated.
First, the Polymorph module in MS program package is employed to search for the most possible spatial packings forε-CL-20 and the above recommended 7 HEDC among seven most possible space groups (P21/c, P-1, P212121, P21, C2/c, Pbca and Pna21), and their reasonable crystal structures are predicted. By comparing the optimized molecular structures from the Dreiding and Compass force fields with that using the DFT-GGA-PBE method, and it is found that the Dreiding force field is suitable for nitro and nitrate compounds, but the Compass for the nitramine and nitrate series. Considering the results from both the two force fields,ε-CL-20, 2,4,6,8-tetranitrohexaadamantane, 2,4,6,8,10-pentanitrohexaazaadamantane, 2,4,6,8,9,10-hexanitrohexaadamantane, and 1,2,4,6,8,9,10-adamantylheptanitrate are predicted to pack in P21/c, P-1, P-1, P21/c, and P21/c space groups, respectively, and 1,2,3,4,5,6,7,8-octanitroadamantane, 1,2,3,4,5,6,7,8,9-nonanitroadamantane, and 1,2,3,4,5,6,7,8,9,10-decanitroadamantane are predicted to crystallize in C2/c, P21/c, and C2/c, respectively.
Second, periodic ab initio calculations are performed to obtain the band structures of the predicted crystals ofε-CL-20 and the seven potential HEDC using the DFT-GGA-PBE method in Dmol3 program package.The method is proved reliable by the similarity of the band structures and density of states (DOS) between the predicted and experimentalε-CL-20 crystal. Seen from the DOS, especially the constitutions of the valence and conductor bands near Fermi energy of each crystal, the N–NO_2, C–NO_2, and O–NO_2 bonds are suggested as the trigger bonds of the nitramine compounds (ε-CL-20 and PNHAA), PNA, and adamantantylnitrates, respectively. This is consistent with both that drawn from the theoretical studies on their gas molecules and experiment. It is strongly suggested that more attention should be paid on the 2,4,6,8,9,10-hexanitrohexaazaadamantane. It has similar DOS and comparable band gap (ΔEg) with those ofε-CL-20, presenting its similar sensitivity withε-CL-20. This agrees well with that drawn from the bond dissociation energy (EN–N) of N–NO_2; meanwhile, due to its larger predicted density (2.315g.cm-3) than that ofε-CL-20 (2.173g.cm-3), it is believed that `if it can be successfully synthesized, its energetic properties may be prior to those ofε-CL-20, which is currently the most heated point.
Finally, periodic ab initio calculations are carried out to obtain the band structures of the four CL-20 existing polymorphs (α·H2O,β,γandε-CL-20), and according to the calculated band gap (?Eg), the sensitivity order of the four polymorphs is predicted asε<β<γ<α·H2O, which is consistent with that by the experiment and the principle of easiest transition (PET). This provides the first example of using the theoretical criterion to predict the sensitivity of molecular crystals. The most stableε-CL-20 crystal is chosen to investigate the influences of pressure on its geometry, electronic structures, and performances. The results show thatε-CL-20 always exhibits its anisotropic properties from lower to higher pressure; when the pressure is at lower than 10 GPa, its cell parameters, band structure, DOS, andΔE_g are little affected by the pressure; while the pressure increases from 10 to 400GPa, these parameters change a lot; and when it is at 400 GPa, theΔE_g trends to be zero, the DOS become smooth curves, and great distortions happened to the dihedral angles of N-NO_2, indicating thatε-CL-20 has already owned some metal properties.
The third part is mostly the MD simulations on the structures and properties of theε-CL-20-based PBX, also named HEDM. The effects of different types of binders, the proportion of binder (W%), temperature (T), crystal defects and so on, on the four basic properties (mechanic properties, energetic properties, compatibility, and safety) are investigated. These provide information and establish the basis for the practical formulation design.
First, based on the“cutting”model, in which four types of fluorine binders, polyvinylidene difluoride (PVDF), polychlorotrifluoroethylene (PCTFE), F2311, and F2314, are put on the three different crystal surfaces (001), (010), and (100) ofε-CL-20 crystal, respectively, and MD simulations are performed on the obtained 12 PBX models. From the static mechanic analysis, their mechanic properties (elastic constants, tensile modulus, bulk modulus, shear modulus, and Poisson’s ratio) are obtained. The results show that the additions of small fluorine binders can improve the mechanical properties ofε-CL-20; due to the higher molecular density on the (001) surface ofε-CL-20, this surface can more strongly interact with the polymer binders, and therefore the binders on the (001) surface can improve more the mechanic properties; among the four binders, the PBX consisting ofε-CL-20 and F2314 has the best comprehensive mechanical properties; and the four binders have similar influences on the energy properties (heat of detonation, detonation velocity, and detonation pressure).
Second, the better model,ε-CL-20(001)/F2314, is selected as an example to investigate the influences of T, W%, and crystal defects (vacancy and doping) on the performances of the PBX by MD simulations. It is found that T has effects on the mechanical properties, but little on the binding energy (Ebind). With W% increasing, the total Ebind between F2314 andε-CL-20 molecules increases, but the average binding energy per polymer chain (Eaver) decreases; the PBX with 4.69% F2314 is found with the better mechanical properties and detonation properties, this proportion (W%)of F2314 matches well with that (<5%) in practical formulation. In terms of the two models of crystals with defects, only the mechanic properties (mainly refers to tensile modulus, bulk modulus, and shear modulus) of the crystal with vacancy and the corresponding PBX change greatly compared with the perfect crystal, but little change happens to the structures and properties of the models with doping.
Third, three types of energetic binders, polyurethane (Estane), glycidyl azide polymer (GAP), and hydroxy terminated polybutadiene (HTPB) are chosen to constituteε-CL-20-based PBX for MD simulations. It is the first time to correlate the binding energies (Ebind) with their physic compatibility between the binders and body explosives, and this well differentiates and interprets the experimental results. By the pair correlation function g(r) analysis, the manners of interactions between the binders andε-CL-20 are revealed. As to theε-CL-20/polyglycol (PEG) PBX, without experiment data is similarly simulated, and its related performances are predicted. Comprehensively comparison of the mechanical and explosive properties among the various simulated PBX will provide information and reference evidence for choosing optimum binder.
In all, in this thesis, based on quantum chemistry, a set of simple and convenient method is developed to evaluate the density (ρ), detonation velocity (D), and detonation pressure(p) of high energy materials; a quantitative standard of energy (ρ, D, and p) and stability(BDE of trigger bond) is suggested to discriminate a practical HEDC; and seven potential HEDC targets are recommended among various derivatives of adamantane and hexaazaadamantane. By combining the MM and QM methods, the space packings and band structures of the predicted crystals for the seven HEDC are predicted, and hexanitrohexaazaadamantane is strongly recommended to synthesize for its performance superior to CL-20. Besides, the MD method is employed to simulate the structures and many performances of various CL-20-based PBX (namely, HEDM) at different temperatures, with different proportions of binder, and with“perfect”or“defective”CL-20 crystal. These provide information and reference in choosing optimum binder and guiding formulation design of HEDM. This work is pioneer and innovative in the front and crossing research field of HEDM, and successfully complete the various tasks assigned by the national defence 973 and National Nature Science Finance Projects.
第一部分是HEDC的“分子设计”。基于量子化学计算首次建议和运用判别HEDC的定量标准(密度ρ>1.9g·cm~(-3),爆速D>9.0km·s~(-1)和爆压p>40.0GPa),并兼顾其稳定性(热解引发键离解能BDE>120kJ·mol~(-1))要求,从上述多系列有机笼状化合物中推荐了7种HEDC。
首先,以量子化学第一性原理DFT-B3LY/6-31G*水平的全优化构型,求得系列多硝基金刚烷(PNA)的红外光谱(IR)和298~800K温度范围的热力学性质(C_(p,m)°、S_m°和H_m°);设计等键反应求得其气相生成热(HOF);按0.001e·Bohr-3电子密度曲面所包含的体积求得晶体理论密度(ρ);按Kamlet-Jacobs方程估算它们的爆速(D)和爆压(p)。运用UHF-PM3方法求得该系列化合物的各可能引发键的均裂活化能(E_a),预测其热解引发机理和稳定性相对大小;在B3LYP/6-31G*水平求得引发键C–NO_2键离解能(EC–N);发现热解引发键的键级(B_(C–NO2))、E_(C–N)、E_a以及–NO_2上净电荷(QNO_2)对判别稳定性或感度的等价线性关系。按照我们建议的HEDC的定量标准和稳定性要求,发现1,2,3,4,5,6,7,8-八硝基金刚烷、1,2,3,4,5,6,7,8,9-九硝基金刚烷和1,2,3,4,5,6,7,8,9,10-十硝基金刚烷三种化合物是值得推荐的潜在HEDC,从而否定了国外前人由基团加和法得出的十一硝基金刚烷是PNA系列最佳HEDC目标物的结论。此外,还对金刚烷的硝酸酯基系列化合物作类似的理论研究,根据判别HEDC的能量与稳定性相结合的定量标准,发现1,2,4,6,8,9,10-七硝酸酯基金刚烷可作为HEDC目标物。
其次,在B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G*水平下,对NO_2气相硝化金刚烷的反应机理进行动态理论计算。求得各可能反应途径的过渡态,通过比较各可能反应途径所需反应势垒(E_a),确定了该反应的最佳途径,所得结论与实验相符,表明理论计算对指导HEDC的实验合成有助。
再次,与研究多硝基金刚烷系列类似,在多硝基六氮杂金刚烷(PNHAA)系列衍生物结构-性能计算研究的基础上,报导了它们按等键反应设计所得生成热(HOF),估算了晶体理论密度(ρ)、爆热(Q)、爆速(D)和爆压(p);通过比较两种可能引发键(C–N和N–NO_2)的键离解能(E_(C–N)和E_(N–NO2)),揭示其热解机理,确定引发键为N–NO_2键;将稳定性或感度与多种理论结构参数进行了关联。类似地,按HEDC的ρ、D、p定量标准和引发键离解能(EN–N)大小,求得含四硝基、五硝基尤其是六硝基六氮杂金刚烷三种化合物为潜在HEDC。
最后,作为PNHAA研究的扩展,对HAA其它三类(即–CN、–NC和–ONO_2基)衍生物进行结构和性能研究,为新型HEDM的分子设计增添了信息和规律。计算结果表明,HAA的–CN和–NC衍生物虽然生成热大、爆热高,但因负氧平衡,其ρ、D和p较低,故不是HEDC。(据此可推测在金刚烷的该两类衍生物中也不可能找到HEDC。) 2,4,6,8-、2,4,6,9-、2,4,6,8,10-和2,4,6,8,9,10-多硝酸酯基HAA虽满足HEDC的ρ、D、p定量标准,但引发键O–NO_2键离解能(EO–N)太小,表明其稳定性极差(如2,4,6,8-四硝酸酯基HAA的EO–N仅为29.81 kJ?mol-1),故它们亦不宜推荐为实用HEDC。
第二部分包括分子堆积方式预测和晶体结构与性能的理论研究。对前述由分子设计求得的七种HEDC进行空间堆积方式预测,并对求得的合理晶型作周期性计算,报导其能带结构和性能。对已获得实用的当前最重要的HEDC—CL-20的四种晶型进行周期性从头计算,并研究了压强对其中最稳定晶型ε-CL-20的影响。
首先,借助MS程序中Polymorph模块,在7种最可几空间群(P21/c、P-1、P212121、P21、C2/c、Pbca和Pna21)中,运用分子力学(MM),对已有实验晶型的ε-CL-20和前面找到的七种潜在HEDC进行最佳分子堆积方式搜索,分别地预测出它们的合理晶型。运用DFT-GGA-RPBE方法和Compass、Dreiding两种力场,求得它们各自的优化构型。经比较表明,Dreiding力场适用于硝基和硝酸酯类化合物,而Compass力场则较为适用于硝胺和硝酸酯类。综合两种力场的预测结果,求得ε-CL-20、2,4,6,8-四硝基六氮杂金刚烷、2,4,6,8,10-五硝基六氮杂金刚烷、2,4,6,8,9,10-六硝基六氮杂金刚烷和1,2,4,6,8,9,10-七硝酸酯金刚烷分别属于P21/c、P-1、P-1、P21/c和P21/c空间群;1,2,3,4,5,6,7,8-八硝基金刚烷、1,2,3,4,5,6,7,8,9-九硝基金刚烷和1,2,3,4,5,6,7,8,9,10-十硝基金刚烷则分别属于C2/c、P21/c和C2/c空间群。
其次,运用Dmol3程序包中DFT-GGA-RPBE方法,对ε-CL-20晶体和七种潜在HEDC的合理预测晶型进行周期性能带结构从头计算。ε-CL-20的预测晶型与实验晶体呈现类似的能带结构和态密度(DOS),表明所使用的方法可靠。考察各晶体的DOS注重分析Feimi能级附近导带和价带的组成,预示硝胺类即ε-CL-20和多硝基六氮杂金刚烷的热解引发键为N–NO_2,预示多硝基和多硝酸酯基金刚烷的热解引发键分别为C–NO_2和O–NO_2,这些均与实验或由气相分子理论计算导致的结论相一致。我们建议要特别关注2,4,6,8,9,10-六硝基六氮杂金刚烷。它的DOS与CL-20的DOS很相似;其带隙ΔEg与ε-CL-20的也接近,预示其感度与ε-CL-20相当,这与由分子中N–NO_2键离解能(E_(N–N))导致的结论相一致;但因其预测密度值(2.315g·cm-3)高于ε-CL-20的密度(2.173g·cm-3),故表明若能成功合成,则其能量性质将优于当前最热门的CL-20。
最后,对实际存在的CL-20的四种晶型(α·H_2O、β、γ和ε-CL-20)进行周期性能带结构从头计算,按带隙(ΔE_g)大小预测其感度排序ε<β<γ<α·H_2O,与实验事实相一致,符合最易跃迁原理(PET),给出了分子型晶体感度理论判别的首例。以最稳定晶型ε-CL-20为例,研究压强对其几何、电子结构和性能的影响。结果表明,由低压到高压,ε-CL-20晶体均呈现一定的各向异性特征;当压强小于10GPa时,晶胞参数、能带、ΔEg和DOS受压强影响较小;而当压强由10GPa增加到400GPa时,这些参数均发生较大变化;且当压强为400GPa时,带隙趋近于零,DOS呈平缓曲线,分子的N–NO_2二面角发生很大扭曲,表明ε-CL-20已具某些金属属性。
第三部分用分子动力学(MD)方法模拟研究了ε-CL-20基PBX亦即HEDM的结构和性能。考察了黏结剂种类、黏结剂含量(W%)、温度(T)和晶体缺陷等因素对四大基本属性(力学性能、能量性质、相容性和安全性)的影响,为实际配方设计提供信息、奠定基础。
首先,按“切割分面”模型,将四种氟聚物惰性黏结剂:聚偏二氟乙烯(PVDF)、聚三氟氯乙烯(PCTFE)、F2311和F2314分别置于ε-CL-20的3个不同晶面(001)、(010)和(100)上,对所得十二种PBX模型进行MD模拟。基于静态力学分析,求得它们的力学性能(弹性系数、拉伸模量、体模量、剪切模量和泊松比)。结果表明,加入少量氟聚物即能有效改善ε-CL-20的力学性能;因ε-CL-20的(001)面分子密度较大,与黏结剂相互作用较强,故其对力学性能的改善效应也较强;在四种黏结剂中,以F2314与ε-CL-20构成的PBX的综合力学性能较好;四种黏结剂对ε-CL-20的爆炸性质(爆热、爆速和爆压)影响较小,且彼此相差不大。
其次,选取上述较佳PBX模型ε-CL-20(001)/F2314为例,通过MD模拟,探讨了T、W%和晶体缺陷(空位和掺杂)对PBX性能的影响。结果表明,T对力学性能有一定影响,而对结合能(E_(bind))影响较小。随W%增加,F_(2314)与ε-CL-20分子间的总结合能(E_(bind))增加,但单根F_(2314)链对应的平均结合能(E_(aver))却降低;含4.69%F_(2314)的PBX具有较好的力学性能和爆轰性能,与实际配方中黏结剂含量(小于5%)相符。就我们所取两种ε-CL-20晶体缺陷模型而言,与“完美”晶体相比,空位缺陷及其相应PBX的力学性能(主要指拉伸模量、体模量和剪切模量)变化较大,而掺杂模型的结构和性能变化较小。
最后,选择三种不同类型的含能黏结剂[聚氨基甲酸乙酯(Estane)、聚叠氮甘油醚(GAP)和端羟基聚丁二烯(HTPB)]与ε-CL-20构成PBX进行MD模拟。首次把模拟所得黏结剂与主体炸药之间的结合能(E_(bind)),与它们之间的物理相容性进行关联,判别并解释了相容性实验结果。通过对相关函数g(r)分析,揭示了各黏结剂与ε-CL-20之间相互作用的方式。对于尚无实验结果的ε-CL-20/聚乙二醇(PEG)PBX进行类似的MD模拟,预测了它的相关性能。综合比较模拟所得多种PBX的力学、爆炸和安全性能,为优选黏结剂提供了信息和参考依据。
总之,本文基于量子化学发展了一套计算高能物质密度(ρ)、爆速(D)和爆压(p)的简便方法,建议了判别HEDC的能量(ρ、D、p)和稳定性(引发键BDE)相结合的定量标准,在多取代基金刚烷和六氮杂金刚烷多系列高能衍生物中,找到了七种HEDC潜在目标物。运用MM和QM相结合的方法,预测了这七种HEDC分子的空间排列方式和晶体能带结构,特别推荐合成性能将优于CL-20的六硝基六氮杂金刚烷。还以MD方法模拟研究了以CL-20为基的多种PBX(亦即HEDM)在不同温度、浓度以及晶体“完美”和“缺陷”条件下的结构和多种性能,为优选黏结剂、进行HEDM配方设计提供了信息和指导。这些工作在HEDM多学科交叉前沿研究领域中具有开拓创新性,圆满地完成了国防973和国家自然科学基金等项目赋予的各项任务。
The dissertation is devoted to systematic researches on the structures and properties of the two types of important organic cage compounds (a series of the high energy derivatives of adamantane and hexaazaadamantane) and the well-known high energy density compound (HEDC) hexanitrohexaazaisowurtzitane (CL-20), using the theoretical and computational chemistry methods, mainly including quantum mechanics (QM), molecular mechanics (MM), molecular dynamics (MD) and so on. We have completed the whole process of searching for high energy density materials (HEDM) from gas molecules to crystal structures, and then to complex materials (such as polymer bonded explosives, PBX). The dissertation is divided into three parts:
The first part concentrates on the“molecular design”of HEDC. Based on the QM calculations, both the quantitative standard (densityρ>1.9g·cm~(-3), detonation velocity D>9.0km·s~(-1), and detonation pressure p>40.0GPa.) as an HEDC and the stability requirement (the dissociation energy of trigger bond, BDE>120kJ·mol~(-1)) are first time suggested to screen out seven potential HEDC from the above referred organic cage compounds.
First, based on the fully optimized structures at the DFT-B3LYP/6-31G* level, the infrared (IR) spectra and thermodynamic properties (C_(p,m)°, S_m°, and H_m°) in the range of 298~800K are computed for polynitroadamantanes (PNA); their gas heats of formation (HOF) are obtained by designing isodesmic reactions; according to the volume inside a contour of 0.001e·Bohr~(-3), their theoretical crystal densities (ρ) are evaluated; and their D and p are estimated according to the Kamlet-Jacobs equations. The UHF-PM3 method is employed to evaluate the activation energy (Ea) for the homolysis of each possible trigger bond, and to predict the pyrolysis initiation mechanism and relative stability of PNA; the dissociation energy (E_(C–N)) of each trigger bond C–NO_2 is calculated at the B3LYP/6-31G* level; and it is found that all the bond order of the trigger bond (BC–N), EC–N, Ea, and the net charge on–NO_2 (QNO_2) can be equally used to predict the stability or sensitivity of PNA. According to the suggested quantitative standard and stability requirement as an HEDC, 1,2,3,4,5,6,7,8-octanitroadamantane, 1,2,3,4,5,6,7,8,9-nonanitr -oadamantane, and 1,2,3,4,5,6,7,8,9,10-decanitroadamantane are worth recommending as potential HEDC, and this denies the foreigners’conclusion from group additivity method that the PNA with 11 nitro groups was the target compound. Besides, similar studies are carried out on the–ONO_2 derivatives of adamantane; and in the light of the standard, 1,2,4,6,8,9,10-adamantylheptanitrate also is considered as an HEDC candidate.
Second, at the B3LYP/6-311++G(3df,2pd)//B3LYP/6-31G* level, the reaction mechanism on the nitration of adamantane with NO_2 is investigated. All the transition states of each possible reaction path are found, and the most possible reaction path is confirmed by comparing each reaction barrier (Ea). The obtained conclusion agrees well with that from the experiment, presenting the availability of theoretical computation in guiding HEDC synthesis.
Third, in the same way, on the basis of the studies on the structures and properties of the polynitrohexaazaadamantanes (PNHAA), their HOF obtained by isodesmic reaction are reported; theirρ, D and p are evaluated; by comparing the dissociation energies (EC–N and EN–N) of two possible trigger bonds (C–N and N–NO_2), their thermolysis mechanisms is revealed, and the N–NO_2 bond is predicted as the trigger bond; their stability or sensitivity has been correlated with various theoretical structure parameters. Similarly, according to theρ, D and p criteria as an HEDC and the value of EN–N, three PNHAA with 4, 5 and 6–NO_2 are recommended as the potential HEDC.
Finally, as an extension of the studies on PNHAA, further studies on the structures and properties of the other three kinds of HAA derivatives (–CN,–NC, and–ONO_2) are made to provide more basis data for the molecular design of new type of HEDM. The calculation results indicate that although the–CN and–NC derivatives of HAA show high heats of formation and high heats of detonation, they cannot meet the criteria as an HEDC, due to their negative oxygen balances and lowerρ, D and p. (Accordingly, none of these two types of adamantane derivatives can be predicted as HEDC). 2,4,6,8-, 2,4,6,8,10-, and 2,4,6,8,9,10-hexaazaadamantylnitrates satisfy theρ, D, and p standard as an HEDC, their dissociation energies (EO–N) of trigger bond O–NO_2, however, are too small (for example, EO–N of 2,4,6,8-hexaazaadamantyltetranitrate is only 29.81 kJ.mol-1), thus they all cannot be recommended as practical HEDC, too.
The second part focuses on molecular packing predictions and theoretical studies on the structures and performance of crystals. The predictions of spacial packing are made for the seven HEDC obtained from the above molecular design; and the band structures and performances of the reasonably predicted crystals are calculated from periodic calculations. Periodic Ab inito calculations are also carried out on the four polymorphs of the currently most important HEDC–CL-20, and the influences of pressure on the most stableε-CL-20 crystal is investigated.
First, the Polymorph module in MS program package is employed to search for the most possible spatial packings forε-CL-20 and the above recommended 7 HEDC among seven most possible space groups (P21/c, P-1, P212121, P21, C2/c, Pbca and Pna21), and their reasonable crystal structures are predicted. By comparing the optimized molecular structures from the Dreiding and Compass force fields with that using the DFT-GGA-PBE method, and it is found that the Dreiding force field is suitable for nitro and nitrate compounds, but the Compass for the nitramine and nitrate series. Considering the results from both the two force fields,ε-CL-20, 2,4,6,8-tetranitrohexaadamantane, 2,4,6,8,10-pentanitrohexaazaadamantane, 2,4,6,8,9,10-hexanitrohexaadamantane, and 1,2,4,6,8,9,10-adamantylheptanitrate are predicted to pack in P21/c, P-1, P-1, P21/c, and P21/c space groups, respectively, and 1,2,3,4,5,6,7,8-octanitroadamantane, 1,2,3,4,5,6,7,8,9-nonanitroadamantane, and 1,2,3,4,5,6,7,8,9,10-decanitroadamantane are predicted to crystallize in C2/c, P21/c, and C2/c, respectively.
Second, periodic ab initio calculations are performed to obtain the band structures of the predicted crystals ofε-CL-20 and the seven potential HEDC using the DFT-GGA-PBE method in Dmol3 program package.The method is proved reliable by the similarity of the band structures and density of states (DOS) between the predicted and experimentalε-CL-20 crystal. Seen from the DOS, especially the constitutions of the valence and conductor bands near Fermi energy of each crystal, the N–NO_2, C–NO_2, and O–NO_2 bonds are suggested as the trigger bonds of the nitramine compounds (ε-CL-20 and PNHAA), PNA, and adamantantylnitrates, respectively. This is consistent with both that drawn from the theoretical studies on their gas molecules and experiment. It is strongly suggested that more attention should be paid on the 2,4,6,8,9,10-hexanitrohexaazaadamantane. It has similar DOS and comparable band gap (ΔEg) with those ofε-CL-20, presenting its similar sensitivity withε-CL-20. This agrees well with that drawn from the bond dissociation energy (EN–N) of N–NO_2; meanwhile, due to its larger predicted density (2.315g.cm-3) than that ofε-CL-20 (2.173g.cm-3), it is believed that `if it can be successfully synthesized, its energetic properties may be prior to those ofε-CL-20, which is currently the most heated point.
Finally, periodic ab initio calculations are carried out to obtain the band structures of the four CL-20 existing polymorphs (α·H2O,β,γandε-CL-20), and according to the calculated band gap (?Eg), the sensitivity order of the four polymorphs is predicted asε<β<γ<α·H2O, which is consistent with that by the experiment and the principle of easiest transition (PET). This provides the first example of using the theoretical criterion to predict the sensitivity of molecular crystals. The most stableε-CL-20 crystal is chosen to investigate the influences of pressure on its geometry, electronic structures, and performances. The results show thatε-CL-20 always exhibits its anisotropic properties from lower to higher pressure; when the pressure is at lower than 10 GPa, its cell parameters, band structure, DOS, andΔE_g are little affected by the pressure; while the pressure increases from 10 to 400GPa, these parameters change a lot; and when it is at 400 GPa, theΔE_g trends to be zero, the DOS become smooth curves, and great distortions happened to the dihedral angles of N-NO_2, indicating thatε-CL-20 has already owned some metal properties.
The third part is mostly the MD simulations on the structures and properties of theε-CL-20-based PBX, also named HEDM. The effects of different types of binders, the proportion of binder (W%), temperature (T), crystal defects and so on, on the four basic properties (mechanic properties, energetic properties, compatibility, and safety) are investigated. These provide information and establish the basis for the practical formulation design.
First, based on the“cutting”model, in which four types of fluorine binders, polyvinylidene difluoride (PVDF), polychlorotrifluoroethylene (PCTFE), F2311, and F2314, are put on the three different crystal surfaces (001), (010), and (100) ofε-CL-20 crystal, respectively, and MD simulations are performed on the obtained 12 PBX models. From the static mechanic analysis, their mechanic properties (elastic constants, tensile modulus, bulk modulus, shear modulus, and Poisson’s ratio) are obtained. The results show that the additions of small fluorine binders can improve the mechanical properties ofε-CL-20; due to the higher molecular density on the (001) surface ofε-CL-20, this surface can more strongly interact with the polymer binders, and therefore the binders on the (001) surface can improve more the mechanic properties; among the four binders, the PBX consisting ofε-CL-20 and F2314 has the best comprehensive mechanical properties; and the four binders have similar influences on the energy properties (heat of detonation, detonation velocity, and detonation pressure).
Second, the better model,ε-CL-20(001)/F2314, is selected as an example to investigate the influences of T, W%, and crystal defects (vacancy and doping) on the performances of the PBX by MD simulations. It is found that T has effects on the mechanical properties, but little on the binding energy (Ebind). With W% increasing, the total Ebind between F2314 andε-CL-20 molecules increases, but the average binding energy per polymer chain (Eaver) decreases; the PBX with 4.69% F2314 is found with the better mechanical properties and detonation properties, this proportion (W%)of F2314 matches well with that (<5%) in practical formulation. In terms of the two models of crystals with defects, only the mechanic properties (mainly refers to tensile modulus, bulk modulus, and shear modulus) of the crystal with vacancy and the corresponding PBX change greatly compared with the perfect crystal, but little change happens to the structures and properties of the models with doping.
Third, three types of energetic binders, polyurethane (Estane), glycidyl azide polymer (GAP), and hydroxy terminated polybutadiene (HTPB) are chosen to constituteε-CL-20-based PBX for MD simulations. It is the first time to correlate the binding energies (Ebind) with their physic compatibility between the binders and body explosives, and this well differentiates and interprets the experimental results. By the pair correlation function g(r) analysis, the manners of interactions between the binders andε-CL-20 are revealed. As to theε-CL-20/polyglycol (PEG) PBX, without experiment data is similarly simulated, and its related performances are predicted. Comprehensively comparison of the mechanical and explosive properties among the various simulated PBX will provide information and reference evidence for choosing optimum binder.
In all, in this thesis, based on quantum chemistry, a set of simple and convenient method is developed to evaluate the density (ρ), detonation velocity (D), and detonation pressure(p) of high energy materials; a quantitative standard of energy (ρ, D, and p) and stability(BDE of trigger bond) is suggested to discriminate a practical HEDC; and seven potential HEDC targets are recommended among various derivatives of adamantane and hexaazaadamantane. By combining the MM and QM methods, the space packings and band structures of the predicted crystals for the seven HEDC are predicted, and hexanitrohexaazaadamantane is strongly recommended to synthesize for its performance superior to CL-20. Besides, the MD method is employed to simulate the structures and many performances of various CL-20-based PBX (namely, HEDM) at different temperatures, with different proportions of binder, and with“perfect”or“defective”CL-20 crystal. These provide information and reference in choosing optimum binder and guiding formulation design of HEDM. This work is pioneer and innovative in the front and crossing research field of HEDM, and successfully complete the various tasks assigned by the national defence 973 and National Nature Science Finance Projects.
引文
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