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Thermal hazard evaluation of AIBME by micro-calorimetric technique coupled with kinetic investigation

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Abstract

2,2′-Azobis (2-methylpropionate) (AIBME) is a new type of environmental-friendly oil-soluble azo initiator, extensively applied in the radical polymerization industry relying on its extraordinary thermal and physicochemical properties. Nevertheless, the special structure makes AIBME decompose easily under low ambient temperature with a tremendous amount of heat release. To qualify its thermal hazard and obtain the specific safety parameters such as time to maximum rate under adiabatic condition (TMRad) and self-accelerating decomposition temperature (SADT), differential scanning calorimeter (DSC), simultaneous thermogravimetric analyzer (STA), and accelerating rate calorimeter (ARC) were applied to analyze the thermal behaviors of AIBME while conducting the thermokinetic analysis and numerical curve fitting. The results indicate that AIBME decomposes at low temperature, and the SADT of AIBME in 25 kg UN package is 35.2 °C. Moreover, the temperature at TMRad = 8 h is determined at 51.6 °C using Townsend method. Compared with commercially used azo compounds, such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2-azobis(2-methylbutyronitrile) (AMBN)), the predominant heat of decomposition, more gaseous degradation products, quicker heat release rate, and lower decomposition temperature make AIBME more hazardous during production, storage, and transportation. The results of this study can provide the references for the process safety assessment and the design of appropriate safety system in scale-up applications with the wish to avoid the occurrence of AIBME involved accidents.

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Abbreviations

A :

Pre-exponential factor (s−1)

C p :

Total heat capacity (kJ kg−1 K−1)

C pB :

Bomb heat capacity (kJ kg−1 K−1)

C ps :

Sample heat capacity (kJ kg−1 K−1)

C 0 :

Initial concentration of the reaction (mol L−1)

(dT dt−1)max :

Maximum temperature rise rate (°C min−1)

(dP dt−1)max :

Maximum pressure rise rate (bar min−1)

E a :

Apparent activation energy (kJ mol−1)

k :

Rate constant (min−1)

m B :

Bomb mass (g)

m s :

Sample mass (g)

M T :

Self-heating rate measured at temperature T (°C min−1)

M m :

Maximum self-heating rate (°C min−1)

n :

Reaction order (dimensionless)

P :

Pressure (bar)

P f :

Final pressure (bar)

R :

Gas constant (8.314 J mol−1 K−1)

S :

Contact area of the system and environment (m2)

SADT :

Self-accelerating decomposition temperature (°C)

t :

Time (min)

t m :

Time at maximum temperature (min)

T :

Temperature (°C)

T on :

Onset temperature in DSC (°C)

T 0 :

Initial temperature in ARC (°C)

T p :

Peak temperature (K)

T f :

Final temperature (°C)

T m :

Maximum temperature (K)

TMR ad :

Time to maximum rate under adiabatic conditions (min)

T D8 :

Temperature at TMRad = 8 h (°C)

T D24 :

Temperature at TMRad = 24 h (°C)

T NR :

Temperature of no return (K)

U :

Heat transfer coefficient (J m−2 K−1 s−1)

W p :

Peak power at time (W g−1)

α :

Conversion degree (dimensionless)

β :

Heating rate (°C min−1)

τ :

Time constant (min)

Φ :

Thermal inertia (dimensionless)

ΔHd :

Heat of decomposition (J g−1)

ΔHad :

Heat of adiabatic reaction

ΔT :

Temperature rise (°C)

ΔTab :

Absolute temperature rise (°C)

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Acknowledgements

The authors would like to express their appreciation to the Anhui Provincial Natural Science Foundation, China (No. 1908085ME125), Anhui Province Education Department Natural Sciences Key Fund, China (No. KJ2017A078), and Jiangsu Province Petrochemical Safety and Environmental Engineering Research Center, China (No. 35541319022) for the financial support of this study.

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Authors and Affiliations

  1. School of Chemical Engineering, Anhui University of Science and Technology, Huainan, 232001, Anhui, China

    Shang-Hao Liu, Yi-Ming Lu, Zhi-Ling Xu & Tong Wu

  2. Jiangsu Province Petrochemical Safety and Environmental Engineering Research Center, Changzhou, 213164, Jiangsu, China

    Shang-Hao Liu

  3. School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, Liaoning, China

    Xiao-Bing Zhan

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  1. Shang-Hao Liu
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Liu, SH., Zhan, XB., Lu, YM. et al. Thermal hazard evaluation of AIBME by micro-calorimetric technique coupled with kinetic investigation. J Therm Anal Calorim 141, 1443–1452 (2020). https://doi.org/10.1007/s10973-019-09116-5

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