Method for calculating impact sensitivity of layered energetic material
By constructing an impact sensitivity calculation model for layered energy-containing materials, using surface electrostatic potential charge equilibrium, crystal density and hydrogen bond energy, the problem of inaccurate prediction of impact sensitivity in the prior art is solved, and the layered energy-containing materials are realized security judgment and model verification.
Patent Information
- Application Number
- CN202411113527.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-07-23
- Filing Date
- 2024-08-14
- Publication Date
- 2024-12-10
AI Technical Summary
The lack of accurate theoretical models in the prior art to predict the impact sensitivity of layered energy-containing materials, resulting in obstacles in the development of new low-sensitivity layered energy-containing materials.
A calculating model of impact sensitivity of layered energy-containing materials was constructed. By obtaining the surface electrostatic potential charge equilibrium, crystal density and hydrogen bond energy, a ternary linear regression model was established, and the existing software was used to optimize molecular structure and calculation parameters to predict impact. Sensitivity.
The impact sensitivity prediction of layered energy-containing materials before the experiment is achieved, the safety of the layered energy-containing materials is judged, and the accuracy of the model is verified in the examples, ensuring the safety and rationality of the design.
Smart Images
Figure CN119108028A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for determining the impact sensitivity of a layered energetic material, and in particular to a method for constructing a layered energetic material impact sensitivity calculation model and an impact sensitivity calculation method. Background Art
[0002] Layered energetic materials are a type of crystalline energetic materials with layered stacking characteristics formed by planar organic energetic molecules through intermolecular interactions such as hydrogen bonding and π-π stacking. They are low-sensitivity high-energy materials with great potential. The molecular structure and stacking pattern of the typical layered energetic material TATB can be seen in Figure 1 As shown. Although the impact sensitivity of layered energetic materials is often low, the factors affecting their impact sensitivity are not only determined by the stacking pattern of the crystal. Therefore, there are also some problems with the high impact sensitivity of layered energetic materials. Therefore, it is extremely important to theoretically predict the impact sensitivity of layered energetic materials. First, the synthesis steps of layered energetic materials are cumbersome and there is a great difficulty in synthesis. Second, the process of crystal formation of layered energetic materials is difficult to control. Therefore, it is very necessary to establish a reasonable impact sensitivity prediction model for this type of structure.
[0003] At present, there is no theoretical model that can accurately predict the impact sensitivity of layered energetic materials, which poses a constraint on the development of new low-sensitivity layered energetic materials. Summary of the invention
[0004] In view of the defects or shortcomings of the prior art, the present invention firstly provides a method for constructing an impact sensitivity calculation model of layered energetic materials.
[0005] To this end, the method for constructing the impact sensitivity calculation model of layered energetic materials provided by the present invention includes:
[0006] (1) Obtain the surface electrostatic potential charge balance v of a plurality of known layered energetic material molecules; obtain the crystal density value ρ of the corresponding layered energetic material; and calculate the central molecule of the corresponding layered energetic material crystal and the distance from the central molecule The sum of hydrogen bond energies HBE between molecules connected by hydrogen bonds within the range of 1000 to 10000; the impact sensitivity of the corresponding layered energetic material is tested by the impact sensitivity experiment;
[0007] (2) Taking the impact sensitivity as the dependent variable and v, ρ and HBE as the independent variables, the data obtained in step (1) are fitted to obtain a calculation model for the impact sensitivity of layered energetic materials.
[0008] A further specific solution is that the impact sensitivity calculation model of the layered energetic material is as shown in formula (1):
[0009] h 50=-704.693+1533.935*v+198.185*ρ+5.021*HBE (1)
[0010] Among them, h 50 It is the impact sensitivity in cm, which corresponds to the falling height of a 2.5kg hammer used as the impact sensitivity test tool in the impact sensitivity experiment.
[0011] An optional solution is to use quantum chemical calculation methods to optimize the structure of the corresponding layered energetic material molecules and calculate the surface electrostatic potential charge balance v of the optimized molecules. Further optional, the calculation method of v is: use M06-2X-D3 and 6-311G (d, p) in Gaussian16 software to optimize the molecular structure, optimize the molecular structure to the local energy minimum on the potential energy surface, and obtain the wave function file of the optimal molecular structure; use Multiwfn to analyze the wave function file to obtain the surface electrostatic potential charge balance v of the layered energetic material.
[0012] An optional solution is to obtain the crystal structure of the corresponding layered energetic material from the CSD and query the crystal density value ρ of the crystal structure.
[0013] Alternatively, the HBE of the corresponding layered energetic material can be calculated using Crystalexployer17 software.
[0014] The present invention also provides a method for calculating the impact sensitivity of a layered energetic material. The provided method for calculating the impact sensitivity of a layered energetic material includes:
[0015] (1) Calculate the electrostatic potential charge balance v of the molecular surface of the layered energetic material to be predicted, and obtain the crystal density value ρ of the layered energetic material to be predicted; calculate the distance between the central molecule and the central molecule of the crystal of the layered energetic material to be predicted The sum of hydrogen bond energies between molecules connected by hydrogen bonds is HBE;
[0016] (2) The computational model constructed using the above method is used to calculate the impact sensitivity of the layered energetic material to be predicted.
[0017] The present invention can predict the impact sensitivity of the layered energetic material before the experimenter conducts the experiment by calculating the v of the layered energetic material molecule itself, the HBE in the crystal layer and the ρ of the crystal, and can judge whether the designed layered energetic material has a certain degree of safety. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 This is the molecular structure and crystal stacking pattern of the typical layered energetic material TATB (2,4,6-trinitrobenzene-1,3,5-triamine).
[0019] Figure 2 The molecular structures of the layered energetic materials HAFRUF (3,5-dinitro-N-(1H-tetrazol-5-yl)pyridin-2-amine), JARPEB (8-nitro-2-oxo-2-pyrazolo[5,1-d][1,2,3,5]tetrazin-4-amine) and CUFRAZ (N-[4-(5-amino-1,2,4-oxadiazol-3-yl)-1,2,5-oxadiazol-3-yl]nitramide) to be predicted. DETAILED DESCRIPTION
[0020] Unless otherwise specified, the scientific and technical terms used herein are understood according to those skilled in the art.
[0021] The present invention focuses on solving the problem of accurately predicting the impact sensitivity of layered energetic materials. At the same time, for the scientific rationality and interpretability of the model, the multi-level factors that affect the impact sensitivity of layered energetic materials must be fully considered. This is because the structure of layered energetic materials is particular. First, its molecules are planar, and second, there are often strong intermolecular hydrogen bonds between layers. If there are no intermolecular hydrogen bonds in the layered energetic material, it is difficult to ensure low sensitivity. To this end, the prediction model of the present invention is established based on the multi-level influencing factors of the layered energetic material. Specifically, the present invention calculates the surface electrostatic potential charge balance v of the layered energetic material molecules, the center molecule in the layer The nearby intermolecular hydrogen bond energy (HBE) and crystal density (ρ) are used to establish a ternary linear regression model of the above variables and predict the impact sensitivity of the layered energetic material. The parameters involved in the scheme of the present invention can be obtained by known software.
[0022] In order to further understand the invention, the present invention is further described below in conjunction with several typical examples of layered energetic materials, but the present invention is not limited to the following examples. The molecular structure and crystal stacking diagram of the layered energetic materials involved in the examples are shown in Figure 2 The methods are conventional methods unless otherwise specified.
[0023] Embodiment 1:
[0024] This embodiment is based on the existing disclosed layered energetic materials, by collecting and calculating the surface electrostatic potential charge balance v of each known energetic material; obtaining the crystal density value ρ of the corresponding layered energetic material; and respectively calculating the central molecule of the corresponding layered energetic material crystal and the distance from the central molecule The sum of hydrogen bond energies HBE between molecules connected by hydrogen bonds within 10 ...
[0025] Specifically, in the ConQuest software, the Refcode corresponding to the corresponding layered energetic material crystal is input to obtain the crystal structure and the corresponding molecular structure file, and its crystal density is obtained by query;
[0026] The molecular structure of the corresponding energetic material was optimized to the local energy minimum on the potential energy surface using M06-2X-D3 and 6-311+G(d,p) in Gaussian 16 software. The wave function of the optimized structure was analyzed using Multiwfn wave function analysis software to calculate the v of the corresponding layered energetic material.
[0027] The crystals of the corresponding energetic materials were imported into Crystalexployer17 software, and the intermolecular interaction energy was calculated using the B3LYP / 6-31g(d,p) method (here the intermolecular hydrogen bonding energy is represented by the intermolecular interaction energy), and the hydrogen bonding energy of the central molecule was added to obtain the HBE of the corresponding material.
[0028] Then, the impact sensitivity of the layered energetic material h was obtained by performing a three-variable linear regression fitting on the above obtained data with the impact sensitivity as the dependent variable and v, ρ and HBE as the independent variables. 50 The calculation model is as follows:
[0029] h 50 =-704.693+1533.935*v+198.185*ρ+5.021*HBE (1)
[0030] Embodiment 2:
[0031] This embodiment selects the reported HAFRUF energetic crystal, and after an impact sensitivity experiment (corresponding to the impact sensitivity test tool in the impact sensitivity experiment being a 2.5 kg weight falling height), the impact sensitivity of the material is 160 cm.
[0032] The crystal density of HAFRUF obtained by the method described in Example 1 is 1.804 g / cm 3 , v value is 0.21966, and HBE is 31.53 kcal / mol.
[0033] Substituting the obtained parameter value into formula (1) to obtain the impact sensitivity h 50 The value is 148 cm , which is comparable to the experimental value of 160 cm , indicating that the model prediction is reasonable.
[0034] Embodiment 3:
[0035] This embodiment selects the reported JARPEB energetic crystal, and after an impact sensitivity experiment (corresponding to the impact sensitivity test tool in the impact sensitivity experiment being a 2.5 kg weight falling height), the impact sensitivity of the material is 80 cm.
[0036] The crystal density of JARPEB obtained by the method described in Example 1 was 1.884 g / cm 3 , v value is 0.194616, and HBE is 22.64 kcal / mol.
[0037] Substituting the obtained parameters into equation (1) we can get the impact sensitivity h 50 It is 81 cm, which is comparable to the experimental value of 80 cm, indicating that the model prediction is reasonable.
[0038] Embodiment 3:
[0039] This embodiment selects the reported CUFRAZ energetic crystal, and after an impact sensitivity experiment (corresponding to the impact sensitivity test tool in the impact sensitivity experiment being a 2.5 kg weight falling height), the impact sensitivity of the material is 100 cm.
[0040] The crystal density of CUFRAZ obtained by the method described in Example 1 is 1.82 g / cm 3 , v value is 0.173261, and HBE is 37.3 kcal / mol.
[0041] Substituting the obtained parameters into equation (1), we can get the impact sensitivity h of CUFRAZ: 50 It is 109 cm, which is comparable to the experimental value of 100 cm, indicating that the model prediction is reasonable.
Claims
1. A method for constructing a layered energetic material impact sensitivity calculation model, characterized in that the method include: (1) Obtain the surface electrostatic potential charge balance v of a plurality of known layered energetic material molecules; obtain the crystal density value ρ of the corresponding layered energetic material; and calculate the central molecule of the corresponding layered energetic material crystal and the distance from the central molecule The sum of hydrogen bond energies HBE between molecules connected by hydrogen bonds within the range of 1000 to 10000; the impact sensitivity of the corresponding layered energetic material is tested by the impact sensitivity experiment; (2) Taking the impact sensitivity as the dependent variable and v, ρ and HBE as the independent variables, the data obtained in step (1) are fitted to obtain a calculation model for the impact sensitivity of layered energetic materials.
2. The method for constructing the impact sensitivity calculation model of layered energetic materials according to claim 1, characterized in that: The impact sensitivity calculation model of the layered energetic material is shown in formula (1): h 50 =-704.693+1533.935*v+198.185*ρ+5.021*HBE (1) Among them, h 50 It is the impact sensitivity in cm, which corresponds to the falling height of a 2.5kg hammer used as the impact sensitivity test tool in the impact sensitivity experiment.
3. The method for constructing the impact sensitivity calculation model of layered energetic materials according to claim 1, characterized in that: The quantum chemical calculation method is used to optimize the structure of the corresponding layered energetic material molecules and calculate the surface electrostatic potential charge balance v of the optimized molecules.
4. The method for constructing a layered energetic material impact sensitivity calculation model according to claim 1, characterized in that: The calculation method of v is: use M06-2X-D3 and 6-311G (d, p) in Gaussian16 software to optimize the molecular structure, optimize the molecular structure to the local energy minimum on the potential energy surface, and obtain the wave function file of the optimal molecular structure; use Multiwfn to analyze the wave function file to obtain the surface electrostatic potential charge balance degree v of the layered energetic material.
5. The method for constructing the impact sensitivity calculation model of layered energetic materials according to claim 1, characterized in that: The crystal structure of the corresponding layered energetic material is obtained from the CSD and the crystal density value ρ of the crystal structure is queried.
6. The method for constructing a layered energetic material impact sensitivity calculation model according to claim 1, characterized in that: The HBE of the corresponding layered energetic materials was calculated using Crystalexployer17 software.
7. A method for calculating the impact sensitivity of a layered energetic material, characterized in that the method include: (1) Calculate the electrostatic potential charge balance v of the molecular surface of the layered energetic material to be predicted, and obtain the crystal density value ρ of the layered energetic material to be predicted; calculate the distance between the central molecule and the central molecule of the crystal of the layered energetic material to be predicted The sum of hydrogen bond energies between molecules connected by hydrogen bonds is HBE; (2) Calculating the impact sensitivity of the layered energetic material to be predicted using the computational model constructed according to any one of claims 1 to 5.