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. 2023 May 3;14(25):7044-7056.
doi: 10.1039/d3sc01627g. eCollection 2023 Jun 28.

Halogenated PETN derivatives: interplay between physical and chemical factors in explosive sensitivity

Nicholas Lease  1 , Kyle D Spielvogel  1 , Jack V Davis  1 , Jeremy T Tisdale  1 , Lisa M Klamborowski  1 , M J Cawkwell  2 , Virginia W Manner  1
Affiliations

Halogenated PETN derivatives: interplay between physical and chemical factors in explosive sensitivity

Nicholas Lease et al. Chem Sci. .

Abstract

Determining the factors that influence and can help predict energetic material sensitivity has long been a challenge in the explosives community. Decades of literature reports identify a multitude of factors both chemical and physical that influence explosive sensitivity; however no unifying theory has been observed. Recent work by our team has demonstrated that the kinetics of "trigger linkages" (i.e., the weakest bonds in the energetic material) showed strong correlations with experimental drop hammer impact sensitivity. These correlations suggest that the simple kinetics of the first bonds to break are good indicators for the reactivity observed in simple handling sensitivity tests. Herein we report the synthesis of derivatives of the explosive pentaerythritol tetranitrate (PETN) in which one, two or three of the nitrate ester functional groups are substituted with an inert group. Experimental and computational studies show that explosive sensitivity correlates well with Q (heat of explosion), due to the change in the number of trigger linkages removed from the starting material. In addition, this correlation appears more significant than other observed chemical or physical effects imparted on the material by different inert functional groups, such as heat of formation, heat of explosion, heat capacity, oxygen balance, and the crystal structure of the material.

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Conflict of interest statement

There are no conflicts of interest to declare.

Figures

Scheme 1
Scheme 1. Synthesis of Br derivatives of PETN.
Scheme 2
Scheme 2. Synthesis of precursors for iodine derivatives of PETN.
Scheme 3
Scheme 3. Synthesis of the iodine derivatives of PETN.
Scheme 4
Scheme 4. Synthesis of precursors for chlorine derivatives of PETN.
Scheme 5
Scheme 5. Synthesis of chlorine derivatives of PETN.
Scheme 6
Scheme 6. Synthesis of methyl and hydroxyl derivatives of PETN.
Fig. 1
Fig. 1. Molecular structures within single crystals of PETriN-Cl, PETriN-Br, PETriN-I and PETriN-Me.
Fig. 2
Fig. 2. Crystal packing of PETriN-Cl, PETriN-Br, PETRIN-I and PETN.
Fig. 3
Fig. 3. Hirschfield fingerprint plots for PETriN-Cl, PETriN-Br, PETriN-I and PETriN-Me.
Fig. 4
Fig. 4. Heat capacity, oxygen balance, heat of formation, and heat of explosion vs. degrees of substitution on the PETN scaffold.
See this image and copyright information in PMC

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