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

Abstract

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.

Sources of Variation in Drop-Weight Impact Sensitivity Testing of the Explosive Pentaerythritol Tetranitrate

“…Only one of the tests performed at other laboratories used a bare anvil (i.e., without grit paper), although eight tests performed at other laboratories did not indicate whether grit paper was used or not. In these cases, it was assumed that grit paper was used, as its use is the default for drop-weight impact tests. ,,,,, Other parameters in Table that varied widely were drop mass (0.5–4 kg), sample mass (10–35 mg), and methods for determining Go/No-Go. Recall that, at Los Alamos, 40 mg of sample was used with a 2.5 kg drop mass, and Go/No-Go drops were determined using an auditory threshold.…”

“…Although drop-weight impact tests have documented limitations, they are the most common method for measuring explosive sensitivity, and there exists a large collection of impact test results for various explosive materials. Researchers have recently begun collecting and analyzing impact test results in more detail, to better understand the benefits and limitations of impact tests for evaluating material sensitivity. − It is imperative to understand the limitations of drop-weight impact tests when drawing conclusions regarding molecular properties of explosive materials from impact tests, as many recent papers do. − …”

Analysis of Ignition Sites for the Explosives 3,3′-Diamino-4,4′-azoxyfurazan (DAAF) and 1,3,5,7-Tetranitro-1,3,5,7-tetrazoctane (HMX) Using Crush Gun Impact Testing

“…The assumption is that a more sensitive material reacts at a lower drop height (lower input of energy). The determination of a “go” is usually accompanied by a flash of light, the generation of gas, sample expenditure, or a sound recorded on audio instrumentation. − With testing spanning numerous facilities and over 60 years of implementation, large standard deviations exist in collected impact sensitivity data . For example, drop-weight impact measurements of the same energetic materials were shown to have different results when conducted on different instruments. ,− One reason for the discrepancy is that different facilities implement differing means for determining the reaction of the sample, or a “go”. , It has also been shown that a considerable fraction of the available drop energy is partitioned into the elastic deformation of steel striker and anvil components at the moment that ignition occurs; this necessarily implies that the test outcome is not inherent to the explosive alone but is instead highly dependent on the apparatus configuration.…”

Probing of Neural Networks as a Bridge from Ab Initio Relevant Characteristics to Differential Scanning Calorimetry Measurements of High‐Energy Compounds

“…[ 4 ] Functionalized derivatives of the erythritol tetranitrate provide less explosive sensitivity than the pristine material. [ 5 ] New polycyclic N‐oxides based on tetrazine and difurazanopyrazine combine state‐of‐the‐art mechanical insensitivity with thermal stability. [ 6 ] The availability of computer resources has led to an increase in the number of computational predictions of novel HEDMs, supported by a limited number of experimental studies.…”