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Analysis of thermal stability and pyrolysis kinetic of dibutyl phosphate-based ionic liquid through thermogravimetry, gas chromatography/mass spectrometry, and Fourier transform infrared spectrometry

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Abstract

To analyze the feasibility of phosphorus-containing ionic liquids used as flame retardants on flammable materials, thermal stability and pyrolysis kinetics of 1-butyl-3-methylimdazolium dibutyl phosphate ([Bmim][DBP]) were investigated using nonisothermal thermogravimetry. The apparent onset decomposition temperature (T0) and mass fraction of residual carbon were 275.2–297.3 °C (± 0.5 °C) and 8.6–10.2% (± 0.1%), respectively. The apparent activation energy (Ea), pre-exponential factor (A), and most probable kinetic function [G(α)] were calculated using thermokinetic methods as Ea = 152–164 kJ mol−1 (± 2 kJ mol−1), ln A = 27.7 ± 0.4 s−1, and G(α) = − ln(1 − α). The maximum operation temperature was estimated as 166.0 ± 0.2 °C, which was considerably lower than T0. The pyrolysis products were identified through gas chromatograph/mass and Fourier transform infrared spectrometers. As a novel finding, the main flame-retarding mechanism of [Bmim][DBP] occurred primarily in condensed phase. Complementally, [Bmim][DBP] was testified to have the flame-retardant effect on epoxy resin by limited oxygen index and vertical burning tests.

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Abbreviations

A :

Pre-exponential factor (s−1)

α :

Fraction of conversion (mass%)

β :

Heating rate (K min−1)

C :

Constant

C 0.25 :

Reaction order, n = 0.25

C 1 :

First-order reaction

C 3 :

Reaction order, n = 3

dα/dt :

Mass loss rate (mass% min−1)

(dα/dt)0.5 :

Mass loss rate at the conversion of 0.5 (mass% min−1)

D 2 :

Valensi reaction

D 3 :

Jander reaction

3D:

Z–L–T reaction

E a :

Apparent activation energy (kJ mol−1)

f(α):

Most probable kinetic function

G(α):

Integral mechanism function

[Him]+ :

1 H-imidazole

ln A :

Logarithmic pre-exponential factor (s−1)

m :

Fraction of mass residual (mass%)

m/z :

Mass charge ratio (°C)

[MHim]+ :

3-Methyl-1 H-imidazole

[Mim]+ :

Methyl imidazole

MOT:

Maximum operation temperature (°C)

MOT1.0% :

Mass loss less than 1.0% of MOT (°C)

R :

Universal gas constant (8.314 J mol−1 K−1)

R 2 :

Regression coefficient

t :

Time of reaction (min)

T :

Temperature (°C)

T 0.5 :

Temperature at the conversion of 0.5 (°C)

T ed :

End temperature (°C)

T m :

Maximum temperature (°C)

T 0 :

Apparent onset decomposition temperature (°C)

T p :

Peak temperature (°C)

y 1(α):

Standard curve

y 2(α):

Experimental curve

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Acknowledgements

This study was very grateful to be supported by the Process Safety and Disaster Prevention Laboratory, Postgraduate Research and Practice Innovation Program of Jiangsu Province (KYCX17_0915). The authors appreciate the original suggestions and heartfelt inspiration for provided by the members of IL research groups.

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Authors and Affiliations

  1. College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, Jiangsu Province, China

    Hui-Chun Jiang, Min Hua, Xu-Hai Pan & Jun-Cheng Jiang

  2. Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology (YunTech), 123, University Rd., Sec. 3, Douliou, 64002, Yunlin, Taiwan, ROC

    Wei-Cheng Lin

  3. Jiangsu Key Laboratory of Hazardous Chemical Safety and Control, Nanjing, 210009, Jiangsu Province, China

    Min Hua, Xu-Hai Pan & Jun-Cheng Jiang

  4. Center for Process Safety and Industrial Disaster Prevention, School of Engineering, YunTech, 123, University Rd., Sec. 3, Douliou, Yunlin, Taiwan, ROC

    Chi-Min Shu

  5. Department of Safety, Health, and Environmental Engineering, YunTech, 123, University Rd, Sec. 3, Douliou, Yunlin, Taiwan, ROC

    Chi-Min Shu

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  1. Hui-Chun Jiang
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Correspondence to Xu-Hai Pan or Chi-Min Shu.

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Jiang, HC., Lin, WC., Hua, M. et al. Analysis of thermal stability and pyrolysis kinetic of dibutyl phosphate-based ionic liquid through thermogravimetry, gas chromatography/mass spectrometry, and Fourier transform infrared spectrometry. J Therm Anal Calorim 138, 489–499 (2019). https://doi.org/10.1007/s10973-019-08229-1

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