Theoretical Study on Energetic Materials Containing (Difluoramino)dinitromethyl Substituted Heteroaromatic Rings

doi:10.6023/A24010017

Abstract

In recent decades, the development of traditional energetic materials has encountered a bottleneck. How to continue to improve the energy level and break the bottleneck has become an urgent problem in the field of energetic materials. Fluorine is a stronger oxidizing agent than oxygen, and theoretically the introduction of fluorine can further increase energy density. Thirteen kinds of energetic molecules containing (difluoramino)dinitromethyl substituted heteroaromatic rings were designed. To ensure the possibility of synthesis, all the structural designs are based on existing intermediates and could be transformed into target molecules through mature synthesis methodologies. The molecular structure, initial thermal decomposition mechanism and energy characteristics were studied theoretically with density functional theory (DFT) methods (B3LYP/6-311+G(d,p) and M06-2X/6-311+G(d,p)) using Gaussian16 program. By calculating the mechanism of the initial decomposition reaction, the trigger bond was determined to be one of the C—NO₂ bonds in the (difluoramino)dinitromethyl group. Dynamic stability is evaluated by the energy barrier of the trigger bond breaking. The results show that most of these molecules have sufficient dynamic stability, the initial decomposition reaction barriers are around 30 kcal/mol. The relationship between the molecule structure and the dynamic stability is revealed. The carbon radical center in the transition state is connected with the strong electron-withdrawing groups (-NO₂ and -NF₂) and the heterocyclic ring with a certain electron-donating ability. This is a typical “push-pull” electronic structure, which makes the free radical particularly stable. Therefore, the homo-cleavage energy barrier of the trigger bond is determined by the stabilizing effect of heterocyclic rings on the methyl free radicals. The energy properties of these molecules were theoretically evaluated with nitrate ester plasticized polyether (NEPE) solid propellant formulations using EXPLO5 program. The results show that the specific impulse of one dynamic stable molecule is up to 280.1 s, which is about 8.4 s higher than that of the traditional HMX (Octogen) formulations.

Key words: difluoramino compound, energetic material, solid propellant, specific impulse, theoretical research

Cite this article

Yongkang Cui, Shoufei Cheng, Lin Ling, Yuxue Li, Long Lu. Theoretical Study on Energetic Materials Containing (Difluoramino)dinitromethyl Substituted Heteroaromatic Rings[J]. Acta Chimica Sinica, 2024, 82(4): 377-386.

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Compd.	1-NF₂	2-NF₂	3-NF₂	4-NF₂	5-NF₂	6-NF₂	7-NF₂
ρ/g/cm³)	2.04	2.00	2.04	2.07	2.04	2.04	1.98
C-NF₂ (Å)	1.495	1.490	1.495	1.487	1.488	1.494	1.494
C-NO₂^a (Å)	1.589	1.568	1.593	1.566	1.577	1.565	1.566
Compd.	8-NF₂	9-NF₂	10-NF₂	11-NF₂	12-NF₂	13-NF₂
ρ/g/cm³)	1.93	1.96	1.98	2.10	2.05	2.08
C-NF₂ (Å)	1.484	1.493	1.492	1.489	1.492	1.491
C-NO₂^a (Å)	1.599	1.569	1.556	1.589	1.569	1.558

Compd.	1-NF₂	2-NF₂	3-NF₂	4-NF₂	5-NF₂	6-NF₂	7-NF₂
ρ/g/cm³)	2.04	2.00	2.04	2.07	2.04	2.04	1.98
C-NF₂ (Å)	1.495	1.490	1.495	1.487	1.488	1.494	1.494
C-NO₂^a (Å)	1.589	1.568	1.593	1.566	1.577	1.565	1.566
Compd.	8-NF₂	9-NF₂	10-NF₂	11-NF₂	12-NF₂	13-NF₂
ρ/g/cm³)	1.93	1.96	1.98	2.10	2.05	2.08
C-NF₂ (Å)	1.484	1.493	1.492	1.489	1.492	1.491
C-NO₂^a (Å)	1.599	1.569	1.556	1.589	1.569	1.558

Compd.	1-NF₂	2-NF₂	3-NF₂	4-NF₂	5-NF₂	6-NF₂	7-NF₂
Energy Barrier ΔG	30.5	32.8	30.5	30.0	29.0	32.6	33.2
BDE ΔH	39.0	41.2	38.7	37.3	36.3	40.3	40.6
Compd.	8-NF₂	9-NF₂	10-NF₂	11-NF₂	12-NF₂	13-NF₂
Energy Barrier ΔG	22.1	32.3	31.4	26.1	31.7	31.8
BDE ΔH	27.3	41.3	40.9	33.1	41.3	41.1

Compd.	1-NF₂	2-NF₂	3-NF₂	4-NF₂	5-NF₂	6-NF₂	7-NF₂
Energy Barrier ΔG	30.5	32.8	30.5	30.0	29.0	32.6	33.2
BDE ΔH	39.0	41.2	38.7	37.3	36.3	40.3	40.6
Compd.	8-NF₂	9-NF₂	10-NF₂	11-NF₂	12-NF₂	13-NF₂
Energy Barrier ΔG	22.1	32.3	31.4	26.1	31.7	31.8
BDE ΔH	27.3	41.3	40.9	33.1	41.3	41.1

Compd.	Formula	ΔH_f/ (kJ/mol)	K-J Function		EXPLO5
Compd.	Formula	ΔH_f/ (kJ/mol)	D/(m/s)	P/GPa	D/(m/s)	P/GPa
1-NF₂	C₃F₂N₆O₇	180.1	9117	38.5	8752	35.4
2-NF₂	C₆F₄N₁₀O₁₁	213.7	9294	40.2	8663	34.6
3-NF₂	C₆F₄N₁₂O₁₀	585.7	9515	42.1	9066	38.5
4-NF₂	C₄F₄N₈O₉	–12.9	8927	37.1	8437	33.1
5-NF₂	C₆F₄N₁₀O₁₀	56.2	9190	39.1	8736	35.6
6-NF₂	C₆F₄N₁₀O₁₀	103.0	9227	39.4	8762	35.6
7-NF₂	C₇H₂F₄N₁₀O₁₀	16.2	9232	38.8	8855	39.2
8-NF₂	C₃H₂F₂N₆O₅	–98.5	9160	37.6	8757	37.5
9-NF₂	C₃HF₂N₇O₆	106.2	9203	38.4	8885	36.6
10-NF₂	C₆H₂F₄N₁₂O₈	187.8	9205	38.6	8910	39.0
11-NF₂	C₃F₄N₆O₅	41.3	9217	40.0	8452	34.3
12-NF₂	C₃F₃N₇O₆	177.7	9127	38.7	8640	34.8
13-NF₂	C₆F₆N₁₂O₈	299.2	9356	41.0	8847	37.1

二氟氨基二硝甲基芳香杂环含能材料的理论研究