Explosive molecule design method for coordinating relation between energy and stability of monomolecular and supramolecular explosives

Abstract

The invention discloses an explosive molecule design method for coordinating the relationship between the energy and the stability of single-molecule and supramolecular explosives, which comprises the following steps of: optimizing related parameters through a Lagrange multiplier method, and designing explosive molecules meeting set indexes; by designing the high-energy explosives and the low-sensitivity explosives to form supramolecules, explosives meeting set indexes can also be obtained, the composition and the structure of the explosives can be designed from the molecular level and the supramolecular level, regulation and control of the relation between the energy and the stability of the explosives are achieved, and the explosive performance is improved. And explosive molecules or supermolecules meeting expected indexes of detonation velocity, sensitivity and density indexes are obtained.

Description

Technical Field

[0001] The invention relates to the technical field of high-energy explosives, and in particular to an explosive molecule design method for coordinating the relationship between the energy and stability of single-molecule and supramolecular explosives. Background Art

[0002] There are very high requirements for the synthesis, purification, yield, cost and safety of single molecules of explosives, and the energy and stability of explosives have reached bottlenecks. The formation of supramolecules is a new method for synthesizing explosives. To a certain extent, it is easier to achieve the coordination of energy and stability than single explosives, and the methods and means of forming supramolecules are also constantly improving. For example, high-energy hexanitrohexaazaisowurtzitane (CL-20) and MTNP form a eutectic (supramolecule) through weak interactions between molecules, thereby improving the comprehensive performance of the two, and being able to achieve a detonation velocity ≥ 9000m / s and a density ≥ 1.9g / cm 3 , Sensitivity h 50 The desired goal is ≥60cm; however, there are currently several problems in the supramolecular assembly of explosives: first, the design is mainly based on experience, and there is a lack of corresponding theoretical methods to coordinate the energy and stability of explosives; second, there is a lack of theoretical methods to guide the formation of supramolecular explosives. Summary of the invention

[0003] The purpose of the present invention is to provide a method for designing explosive molecules that coordinates the relationship between the energy and stability of single-molecule and supramolecular explosives in order to solve the above problems. The present invention can obtain the desired energy and stability (detonation velocity ≥ 9000m / s, density ≥ 1.9g / cm 3 , Sensitivity h 50 ≥60cm). This is achieved through explosive molecular design and supramolecular design.

[0004] The Lagrange multiplier method is a method for finding the maximum value of a function using the extreme points of a multivariate function. The energy function D(ν, ρ) and the stability function S(ν, ρ) of explosives are a pair of contradictory but interrelated relationships, and the independent variable electrostatic equilibrium parameter ν and density ρ are intrinsically related to the two. By establishing a suitable Lagrange function that includes the energy function and the stability function, and finding the extreme values ​​of ν and ρ respectively, the optimized parameters can be obtained by solving them. Then, according to these optimized parameters, the explosive single molecule design or supramolecular design can be carried out to obtain the explosive single molecule or supramolecular that meets the set requirements.

[0005] The present invention achieves the above-mentioned purpose through the following technical solutions:

[0006] A method for designing explosive molecules to coordinate the energy and stability relationship of single-molecule and supramolecular explosives comprises the following steps:

[0007] Step 1: Through the optimization and coordination of the Lagrange multiplier method, the desired energy and stability parameter range can be obtained, that is, detonation velocity ≥ 9000m / s, density ≥ 1.9g / cm 3 , Sensitivity h 50 ≥60cm;

[0008] Step 2, construct the Lagrange function:

[0009] L(v,ρ,λ,μ)=D(v,ρ)+λ{S(v,ρ)-60}+μ{ρ(v)-1.90} (1)

[0010] Or L(ν,ρ,λ,μ)=S(ν,ρ)+λ{D(ν,ρ)-9000}+μ{ρ(ν)-1.90} (2)

[0011] The "60" in the equation refers to h 50 ≥60cm; "1.90" means density ≥1.90g / cm 3 , "9000" means that the detonation velocity is ≥ 9000 m / s; L, ν, ρ, λ, μ, D, and S are Lagrange multiplier function, electrostatic equilibrium parameter, density, Lagrange multiplier factor, detonation velocity, energy function, and stability function, respectively;

[0012] Step 3, according to the electrostatic potential Calculate electrostatic equilibrium parameters in is the total deviation, which reflects the variability and magnitude of the molecular surface electrostatic potential, and is defined as:

[0013]

[0014] In the formula, and are the standard positive and negative deviations of the molecular electrostatic potential, respectively; V + (r i ) and V - (r j ) are r i and r j The positive and negative electrostatic potential at v∈(0,0.25], when ν = 0.25; the electrostatic balance parameter can reflect the balance of charge distribution in the explosive molecules. The closer ν is to 0.25, the higher the balance of charge distribution is ( Figure 3 ).

[0015] Step 4: Calculate the detonation velocity using the Kamlet-Jacobs formula and the density using the Rice formula:

[0016]

[0017]

[0018] Step 5, calculate the partial derivative of the Lagrange multiplier function with respect to the electrostatic equilibrium parameter, density and Lagrange multiplier factor:

[0019]

[0020] Solve equation (6) to obtain the optimal parameter range:

[0021]

[0022] Step 6: Calculate the detonation velocity and density according to equations (4) and (5), and calculate the electrostatic equilibrium parameters according to equation (3). If the detonation velocity is ≥ 9000 m / s and the density is ≥ 1.9 g / cm 3 , the electrostatic equilibrium parameter ν of the explosive molecule is in the interval [0.1, 0.13], that is, the designed explosive molecule meets the set target.

[0023] If high explosives are needed (such as CL-20, with a detonation velocity of ~9500m / s and a density of ~2.01g / cm 3 , ν=0.0550) and aromatic energetic molecules (with larger ν values) form supramolecules through molecular assembly, achieving relevant indicators (detonation velocity optimized by Lagrange multiplier method ≥9100m / s, density ≥1.90g / cm 3 , ν≥0.10), then this supramolecule (generally two or three components, the ratio can be 1:1, 1:2, 2:1 and 1:1:1, etc.) may be what is needed. Whether the two can be assembled into a supramolecule depends on whether they meet the similarity requirement between 0.6 and 1.0. When the similarity of the designed explosive molecule is between 0.6 and 1.0; it can be used to assemble into an explosive supramolecule.

[0024] A further approach is to calculate the similarity of each component of the preformed supramolecule:

[0025] The similarity expression is:

[0026]

[0027] Among them, f sim , A s , S a 、MPI、α、νσ tot 2 , A s ∏ respectively represent similarity, molecular surface area, molecular local softness, molecular polarity index, molecular polarizability, and electrostatic potential parameter statistics.

[0028] Whether the two can be assembled into a supramolecular depends on whether they meet the similarity requirement between 0.6 and 1.0. The theoretical detonation velocity of supramolecular explosives is calculated using the nitrogen equivalent method, and the density is calculated according to formula (5);

[0029]

[0030] The target supramolecular system is the one that satisfies the requirements of formula (7).

[0031] The beneficial effects of the present invention are:

[0032] The invention discloses an explosive molecule design method for coordinating the relationship between the energy and stability of single-molecule and supramolecular explosives. By optimizing relevant parameters by the Lagrange multiplier method, explosive molecules that meet set indicators can be designed. By designing high-energy explosives and low-sensitivity explosives to form supramolecular molecules, explosives that meet set indicators can also be obtained. The method of the invention can design the composition and structure of explosives from the molecular level and the supramolecular level, realize the regulation of the relationship between the energy and stability of explosives, and obtain explosive molecules or supramolecular molecules that meet the expected indicators of detonation velocity, sensitivity, and density. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 This is a diagram of the high-energy molecule design process of the present invention.

[0035] Figure 2 Schematic diagram of the CL-20 / MTNP supramolecular assembly system of the present invention.

[0036] Figure 3 are the electrostatic equilibrium parameters of different high-energy molecules of the present invention. DETAILED DESCRIPTION

[0037] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0038] In any embodiment, if Figure 1As shown, a method for designing explosive molecules for coordinating the relationship between energy and stability of single-molecule and supramolecular explosives of the present invention comprises:

[0039] For example, in the existing high energy molecule CL-20 ( Figure 1 Left), cage isomers were obtained by molecular isomerization design ( Figure 1 ) and benzene ring skeleton isomers ( Figure 1 Right), the theoretical detonation velocity, density and electrostatic equilibrium parameters are calculated according to formulas (4), (5) and (3), respectively. Figure 1 The molecules on the right side basically satisfy equation (7) and may be explosive molecules that can meet the target.

[0040]

[0041] In a specific embodiment, Figure 1-2 As shown, a method for designing explosive molecules for coordinating the relationship between energy and stability of single-molecule and supramolecular explosives of the present invention comprises the following steps:

[0042] With high energy CL-20 molecules ( Figure 1 Based on the left), other stable molecules are sought to form supermolecules with it. According to equation (8), CL-20 and The similarity of the above equations is 0.7390, which is between 0.6 and 1.0. The supramolecular structure of CL-20 / MTNP is optimized, and its density is calculated according to equation (5), and the calculated result is 1.951 g / cm 3 ≥1.900g / cm 3 ; The detonation velocity of CL-20 / MTNP supramolecular explosive is calculated according to equation (9), and the result is 9410.5m / s≥9000m / s; The electrostatic equilibrium parameter is calculated according to equation (5), and the result is 0.1018, which is between the interval [0.1, 0.13], and meets the requirements of Lagrange optimization result (7), which may be an explosive supramolecular that meets the set requirements.

[0043] The experimental results show that CL-20 / MTNP supramolecular explosive ( Figure 2 ) performance meets the set indicators (explosion velocity 9350.6m / s≥9000m / s 1.900g / cm 3 , density 1.947g / cm 3 ≥1.900g / cm 3 , sensitivity h 50 =65cm≥60cm), which met the design requirements.

[0044] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can easily think of changes or replacements within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations. In addition, the various different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for designing explosive molecules to coordinate the relationship between energy and stability of single-molecule and supramolecular explosives, characterized in that: The following steps are involved: Step 1: Set the energy and stability parameter range, i.e., detonation velocity ≥ 9000m / s, density ≥ 1.9g / cm 3 , Sensitivity h 50 ≥60cm; Step 2, construct the Lagrange function: L(ν,ρ,λ,μ)=D(ν,ρ)+λ{S(ν,ρ)-60}+μ{ρ(ν)-1.90} (1) Or L(ν,ρ,λ,μ)=S(ν,ρ)+λ{D(ν,ρ)-9000}+μ{ρ(ν)-1.90} (2) The "60" in the equation refers to h 50 ≥60cm; "1.90" means density ≥1.90g / cm 3 , "9000" refers to the detonation velocity v9000m / s; L, ν, ρ, λ, μ, D, and S are the Lagrange multiplier function, electrostatic equilibrium parameter, density, Lagrange multiplier factor, detonation velocity, energy function, and stability function, respectively; Step 3, according to the electrostatic potential Calculate electrostatic equilibrium parameters in is the total deviation, which reflects the variability and magnitude of the molecular surface electrostatic potential, and is defined as: In the formula, and are the standard positive and negative deviations of the molecular electrostatic potential, respectively; V + (r i ) and V - (r j ) are r i and r j The positive and negative electrostatic potential at ν∈(0,0.25], when ν=0.25; Step 4: Calculate the detonation velocity using the Kamlet-Jacobs formula and the density using the Rice formula: Step 5, calculate the partial derivative of the Lagrange multiplier function with respect to the electrostatic equilibrium parameter, density and Lagrange multiplier factor: Solve equation (6) to obtain the optimal parameter range: Step 6: Calculate the detonation velocity and density according to equations (4) and (5), and calculate the electrostatic equilibrium parameters according to equation (3). If the detonation velocity is ≥ 9000 m / s and the density is ≥ 1.9 g / cm 3 ,The electrostatic equilibrium parameter v of the explosive molecule is in the interval [0.1, 0.13], that the designed explosive molecule meets the set target.

2. A method for designing explosive molecules for coordinating the relationship between energy and stability of single-molecule and supramolecular explosives as claimed in claim 1, characterized in that: When the similarity of the designed explosive molecules is between 0.6 and 1.0, they can be used to assemble into explosive supramolecules.

3. A method for designing explosive molecules for coordinating the relationship between energy and stability of single-molecule and supramolecular explosives as claimed in claim 2, characterized in that: Calculate the similarity of each component of the preformed supramolecule: The similarity expression is: Among them, f sim , A s , S a , MPI, a, νσ tot 2 , A s Π are similarity, molecular surface area, molecular local softness, molecular polarity index, molecular polarizability, and electrostatic potential parameter statistics.

4. A method for designing explosive molecules for coordinating the relationship between energy and stability of single-molecule and supramolecular explosives as claimed in claim 3, characterized in that: The theoretical detonation velocity of supramolecular explosives was calculated using the nitrogen equivalent method, and the density was calculated according to equation (5); The target supramolecular system is the one that satisfies the requirements of formula (7).

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