Examining the chemical and structural properties that influence the sensitivity of energetic nitrate esters

Manner, Virginia W.; Cawkwell, Marc; Kober, Edward M.; Myers, Thomas W.; Brown, Geoff W.; Tian, Hongzhao; Snyder, Christopher J.; Perriot, Romain; Preston, Daniel N.

doi:10.1039/c8sc00903a

Cited by 57 publications

(60 citation statements)

References 80 publications

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“…Functionalities like polynitramino [2], nitrate salts [3], amine [4] or nitrocarbamate [5] were introduced. Furthermore, sila [6] and oxophosphine [4] derivatives are known. Herein we report the synthesis of all azido derivatives from pentaerythritol tetranitrate to tetraazidopentaerythritol.…”

Section: Introductionmentioning

confidence: 99%

About the Azido Derivatives of Pentaerythritol Tetranitrate

Lenz

Klapötke

Mühlemann³

et al. 2021

Propellants Explo Pyrotec

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With the first ever synthesis of monoazidopentaerythritol trinitrate, a comparative study of the properties of all azidonitrate derivatives from pentaerythritol tetranitrate (PETN) to tetraazidopentaerythritol (TAPE) was possible. The azides were prepared by halogen azide exchange and the remaining alcohols were then converted into the organic nitrate esters using acetyl nitrate. The resulting compounds pentaerythritol tetranitrate (PETN), monoazidopentaerythritol mononitrate (MAPETN), diazidopentaerythritol dinitrate (DAPEDN), triazidopentaerythritol mononitrate (TAPEMN), tetraazidopentaerythritol (TAPE) were analyzed for their chemical (XRD, NMR, EA, IR) and energetic properties (DTA/DSC, impact and friction sensitivity) and presented for comparison. An interesting trend of decreasing melting points from PETN to the triazide was observed, with the monoazide found to meet the thermal requirements for a melt-castable explosive. The mechanical sensitivities were successfully explained by Hirshfeld analysis. The energetic properties were calculated with the EXPLO5 code and show a decreasing performance towards the highly sensitive tetraazido derivative. Furthermore, PETN was successfully initiated with its tetraazido derivative TAPE.

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Section: Introductionmentioning

confidence: 99%

About the Azido Derivatives of Pentaerythritol Tetranitrate

Lenz

Klapötke

Mühlemann³

et al. 2021

Propellants Explo Pyrotec

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“…27,28 Compound (1) was first reduced using hydrogen gas and Pd/C to synthesize erythritol tetra-amine. The tetraamine was then treated with ethyl chloroformate and sodium hydroxide to generate the tetra-carbamate intermediate (2) which in turn was nitrated with fuming nitric acid and trifluoroacetic anhydride. Finally, the nitrated carbamate intermediate [compound (3)] was reduced using an ammonia/HCl workup yielding the off-white solid product compound (4) (Scheme 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Erythritol tetraazide was synthesized following the known literature procedures. The synthesis procedure and characterization can be found in refs 24, 25. Compound (2). Erythritol tetraazide (1) (2.34 g, 10.5 mmol) was dissolved in 95% ethanol (40 mL).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Explosive handling sensitivity is dictated by numerous molecular and physical properties and determining which factors play specific roles can potentially provide a blueprint for the design of new explosive molecules. Macroscale influences such as electrostatic effects, crystal packing, cocrystallization, and intra- and intermolecular hydrogen bonding − have all been reported to stabilize high energetic materials. More importantly, chemical effects such as thermodynamics, bond dissociation energies, and decomposition pathways can play a major role in the sensitivity of a molecule.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Erythritol Tetranitrate Derivatives: Functional Group Tuning of Explosive Sensitivity

et al. 2020

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Understanding the factors that affect explosive sensitivity is paramount to the safe handling and development of new explosives molecules. Erythritol tetranitrate (ETN) is an explosive that recently has attracted significant attention in the explosives community because of its ease of synthesis and physical properties. Herein, we report the synthesis of ETN derivatives using azide, nitramine, and nitrate ester functional groups. Impact, spark, and friction sensitivity measurements, computationally calculated explosive properties, and the crystal structure analysis of the ETN derivatives are reported. Mixing explosive functional groups led to changes in the explosive sensitivity, explosive performance as well as physical properties including melting point and physical state at room temperature. Overall, we have demonstrated that combining functional groups can enable the tuning of explosive and physical properties of a molecule. This tunability can potentially aid in the development of new explosives in which characteristics are varied to meet certain specifications.

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“…Reactivity is the key property for energetic crystals, which is highly related to the detonation and sensitivity of EMs. Theoretical methods—including Reactive FFs [ 97 , 98 , 99 , 100 ], AIMD [ 101 , 102 , 103 , 104 , 105 , 106 , 107 ], and DFTB-MD [ 108 , 109 , 110 , 111 , 112 , 113 , 114 ]—were utilized to reveal reaction mechanism of energetic crystals, and ReaxFF is the most efficient. The reactive FF is a unique type of molecular FF, which can describe not only the interactions between particles and their movements, but also the chemical bond formation and rapture, namely chemical reactions, in the process.…”

Section: Reactive Forcefields and The Applications For Emsmentioning

confidence: 99%

Molecular Forcefield Methods for Describing Energetic Molecular Crystals: A Review

et al. 2022

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Energetic molecular crystals are widely applied for military and civilian purposes, and molecular forcefields (FF) are indispensable for treating the microscopic issues therein. This article reviews the three types of molecular FFs that are applied widely for describing energetic crystals— classic FFs, consistent FFs, and reactive FFs (ReaxFF). The basic principle of each type of FF is briefed and compared, with the application introduced, predicting polymorph, morphology, thermodynamics, vibration spectra, thermal property, mechanics, and reactivity. Finally, the advantages and disadvantages of these FFs are summarized, and some directions of future development are suggested.

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Examining the chemical and structural properties that influence the sensitivity of energetic nitrate esters

Abstract: The sensitivity of explosives is controlled by factors that span from intrinsic chemical reactivity to mesoscale structure, and has been a topic of extensive study for over 50 years.

Cited by 57 publications

References 80 publications

About the Azido Derivatives of Pentaerythritol Tetranitrate

About the Azido Derivatives of Pentaerythritol Tetranitrate

Synthesis of Erythritol Tetranitrate Derivatives: Functional Group Tuning of Explosive Sensitivity

Molecular Forcefield Methods for Describing Energetic Molecular Crystals: A Review

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