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Thermal decomposition mechanism and hazard assessment of di-tert-butyl azodicarboxylate (DBAD)

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Abstract

In this work, we used C80 Micro-calorimeter and STA-FTIR-MS instrument to analyze decomposition mechanism of DBAD and evaluated the thermal hazard by the key index on self-accelerating decomposition temperature (SADT). Based on C80 data, the heat release per unit mass of DBAD is 699.85 ± 52.88 kJ kg−1, and the activation energy calculated by Friedman method ranges from 28.58 to 52.03 kJ mol−1. Besides, the thermal decomposition reaction of DBAD can be described by Zhuralev-Lesokin-Tempelman equation. In summary, the decomposition mechanism of DBAD is as follows: the C–O bond cracks firstly, separating ·C(CH3)3 out, then the C–C bond cracks, separating ·CH3 out; the N=N double bond, C–N bond and C–O bond crack subsequently, separating: N–CO, ·O–CO–N:, HO–CO–N: and ·N=N–CO out, and these radical groups gradually decompose or oxidize into ·CH=CHCH3, ·O–CO/CO2, ·COOH, etc.; finally, all these radical groups dissociate and oxidize into H2O, CO2 and N2. The SADT calculated by Semenov model of DBAD under 25 kg standard package is 63.95 °C.

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Abbreviations

TMRad :

Time to maximum rate under adiabatic conditions (min)

TCL :

Time to conversion limit (day)

δH :

Enthalpy changes (kJ mol−1)

α :

Reaction progress (ratio of reacted material to total material)

f(α):

Mechanism function

E a :

Activation energy (kJ mol−1)

A :

Pre-exponential factor of Arrhenius equation (s−1)

β :

Heating rate (°C min−1)

R :

Gas constant (J mol−1K−1)

y(α):

Definition function of Malek method

R 2 :

Square value of the correlation coefficient

T p :

Decomposition peak temperature of DBAD (°C)

T onset :

Initial decomposition temperature (°C)

H p :

Maximum heat flow rate (mW)

∆H :

Heat release per unit mass (kJ kg−1)

λ :

Wavenumber (cm−1)

c p :

Specific heat of reactant (J mol−1K−1)

M 0 :

Reactant mass (g)

T 0 :

Ambient temperature (K)

U :

Surface heat transfer coefficient (J m−2K−1s−1)

S :

Surface area (m2)

q G :

Heat release curve

q L :

Cooling curve

TNR:

Temperature of no return (°C)

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Funding

This work was supported by National Natural Science Foundation of China, Project 51974166.

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Authors and Affiliations

  1. Nanjing University of Science and Technology, Nanjing, 210094, Jiangsu, China

    Min Jia, Song Guo, Shang Gao & Huiming Sun

  2. China Academy of Safety Science and Technology, Beijing, 100012, China

    Sining Chen

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  1. Min Jia
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  2. Song Guo
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  3. Sining Chen
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Correspondence to Song Guo or Sining Chen.

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Jia, M., Guo, S., Chen, S. et al. Thermal decomposition mechanism and hazard assessment of di-tert-butyl azodicarboxylate (DBAD). J Therm Anal Calorim 148, 4317–4331 (2023). https://doi.org/10.1007/s10973-023-11992-x

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