Thermal hazard analysis and initial decomposition mechanism of 5-(4-pyridyl)tetrazolate-methylene tetrazole

Ni, Lei; Yao, Huifeng; Yao, Xinyu; Jiang, Juncheng; Wang, Zhirong; Shu, Chi‐Min; Pan, Yong

doi:10.1016/j.fuel.2020.117434

Cited by 15 publications

(10 citation statements)

References 34 publications

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“…The E a can be found by the Starink method, as shown in Equation ( 1). Compared with the KAS and FWO methods, the activation energy calculated by it has higher accuracy, which is recommended by ICTAC and is widely used in fine chemical calculations [20][21][22][23].…”

Section: Starink Methodsmentioning

confidence: 99%

Thermal Hazard Evaluation of Tert-Butyl Peroxy-3,5,5-trimethylhexanoate (TBPTMH) Mixed with Acid-Alkali

Xia

Pan

et al. 2022

Materials

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Tert-butyl peroxy-3,5,5-trimethylhexanoate (TBPTMH), a liquid ester organic peroxide, is commonly used as an initiator for polymerization reactions. During the production process, TBPTMH may be exposed to acids and alkali, which may have different effects on its thermal hazard, so it is necessary to carry out a study on the thermal hazard of TBPTMH mixed with acids and alkali. In this paper, the effects of H2SO4 and NaOH on the thermal decomposition of TBPTMH were investigated by differential scanning calorimetry (DSC) and adiabatic calorimetry (Phi-TEC II). The “kinetic triple factors” were calculated by thermodynamic analysis. The results show that the three Ea are 132.49, 116.36, and 118.24 kJ/mol, respectively; thus, the addition of H2SO4 and NaOH increased the thermal hazard of TBPTMH. In addition, the characteristic parameters (time to maximum rate under adiabatic conditions, self-accelerated decomposition temperature) of its thermal decomposition were determined, and the control temperature (45, 40, and 40 °C) of TBPTMH under the action of acid-alkali were further received. This work is expected to provide some guidance for the safe storage, handling, production, and transportation of TBPTMH in the process industry.

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Section: Starink Methodsmentioning

confidence: 99%

Thermal Hazard Evaluation of Tert-Butyl Peroxy-3,5,5-trimethylhexanoate (TBPTMH) Mixed with Acid-Alkali

Xia

Pan

et al. 2022

Materials

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“…[47] prevailing proposed mechanism being a stepwise extrusion of molecular nitrogen for both 1,5-and 2,5-substituted tetrazoles. [49][50][51][52][53] Among these studies, a number of isomerization events are observed involving substituents on the tetrazole moiety, leading to a variety of decomposition pathways. [43] Several considerations were made for explosophore-based featurization of tetrazoles: 1) tetrazoles have two different substitution patterns, 2) tetrazoles can bear varied substituents that influence their energetic properties, and 3) many HEMs contain multiple tetrazole explosophores.…”

Section: Explosophore Featurizationmentioning

confidence: 99%

A Physical Organic Approach towards Statistical Modeling of Tetrazole and Azide Decomposition**

et al. 2023

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Nitrogen atom‐rich heterocycles and organic azides have found extensive use in many sectors of modern chemistry from drug discovery to energetic materials. The prediction and understanding of their energetic properties are thus key to the safe and effective application of these compounds. In this work, we disclose the use of multivariate linear regression modeling for the prediction of the decomposition temperature and impact sensitivity of structurally diverse tetrazoles and organic azides. We report a data‐driven approach for property prediction featuring a collection of quantum mechanical parameters and computational workflows. The statistical models reported herein carry predictive accuracy as well as chemical interpretability. Model validation was successfully accomplished via tetrazole test sets with parameters generated exclusively in silico. Mechanistic analysis of the statistical models indicated distinct divergent pathways of thermal and impact‐initiated decomposition.

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“…35 The decomposition mechanisms of tetrazoles have been previously investigated in a number of experimental and computational studies, with the prevailing decomposition mechanism being a stepwise extrusion of molecular nitrogen for both 1,5-and 2,5substituted tetrazoles (Figure 4A and 4B). 7,8,[36][37][38][39] Among these studies, a number of dynamic isomerization events are observed for various tetrazole substituents (-H, -OR, -NHR), leading to a variety of possible decomposition pathways and rendering the development of generalizable reactivity trends challenging. Furthermore, the existence of two constitutional tetrazole isomers (i.e., 1,5-and 2,5-tetrazoles) requires separate mechanistic consideration in the context of a traditional mechanistic study, and the generality of trends observed in such studies would be challenged by the diversity of substituents encountered in tetrazole energetics.…”

Section: Qspr For Tetrazole Hemsmentioning

confidence: 99%

“…To adequately parametrize both tetrazole substitution patterns, we constructed descriptors based on a mechanistic analysis of reported decomposition mechanisms of 1,5-and 2,5-tetrazoles and devised a numbering scheme for shared bonds and common features for tetrazoles of either substitution pattern (Figure 4A and 4B). 7,8,[36][37][38][39] Notably, several key features are maintained regardless of the tetrazole substitution pattern: the bond broken in a stepwise extrusion of molecular nitrogen is the single bond between N 2 and N 3 , a triple bond is formed between N 1 and N 2 in the liberation of nitrogen, N 3 substituted with R 1 and has a lone pair, and there is a double bond between C 4 and N 5 . Recognition of these similarities allowed for a universal description of the tetrazole system through the framework of our descriptor collection workflow.…”

Section: Qspr For Tetrazole Hemsmentioning

confidence: 99%

“…42 This statistical model is consistent with the main decomposition pathway proposed in literature, which features a rate-limiting cleavage of the N 2 -N 3 bond followed by nitrogen extrusion from the ring-opened intermediate (Figure 4A and 4B). 7,8,[36][37][38][39] Electron-demanding substituents at the R 1 and R 2 positions stabilize the ensuing formal negative charge on the C 4 -N 5 motif and a sterically hindered R1 substituent favors the rupture of the ring near N 3 .…”

Section: Qspr For Tetrazole Hemsmentioning

confidence: 99%

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An Explosophore-Based Approach Towards the Prediction of Energetic Material Sensitivity Properties

Rein

Meinhardt

Wahlman

et al. 2021

Preprint

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Accurate prediction of the sensitivity properties of high-energy materials (HEMs) and the study of their decomposition mechanisms are two major focuses within energetics research. Due to the hazards associated with the synthesis and handling of energetic materials, predictive models for HEM sensitivity are of great importance in enabling the safe and efficient development of future HEMs. Traditional predictive modeling of HEM decomposition via machine learning algorithms generally displays limited interpretability, while mechanistic studies of HEMs typically focus on small subsets of structurally analogous compounds lacking generalizability. This study aims to bridge the gap between predictive modeling and computational mechanistic analysis of HEMs, with the goal of providing chemically interpretable models for HEM sensitivity property prediction. Herein, we disclose the use of multivariate linear regression (MLR) modeling for the prediction of the decomposition temperature and impact sensitivity of HEMs. We report an explosophore-based approach to sensitivity property prediction featuring an ensemble of quantum mechanical parameters and computational workflows that enable rapid parameterization and modeling of energetic functional groups. We then employ these methods to accurately predict sensitivity properties of nitrogen-rich tetrazole and azide HEMs. These statistical MLR models are readily interpreted based on the principles of physical organic chemistry, producing structure-property relationships to guide the rational design of new HEMs. Furthermore, we extend our explosophore-based approach to predict the sensitivity properties of HEMs containing multiple, non-equivalent energetic functional groups through the identification of molecular triggers for the bulk decomposition of HEMs. Finally, we showcase the viability of our methods towards ab initio virtual screening of HEMs through predictive modeling of external test sets of tetrazole HEMs using structures and parameters generated exclusively in silico.

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Thermal hazard analysis and initial decomposition mechanism of 5-(4-pyridyl)tetrazolate-methylene tetrazole

Cited by 15 publications

References 34 publications

Thermal Hazard Evaluation of Tert-Butyl Peroxy-3,5,5-trimethylhexanoate (TBPTMH) Mixed with Acid-Alkali

Thermal Hazard Evaluation of Tert-Butyl Peroxy-3,5,5-trimethylhexanoate (TBPTMH) Mixed with Acid-Alkali

A Physical Organic Approach towards Statistical Modeling of Tetrazole and Azide Decomposition**

An Explosophore-Based Approach Towards the Prediction of Energetic Material Sensitivity Properties

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