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Kinetic analysis of the spontaneous thermal polymerization of acrylic acid

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Abstract

Acrylic acid is a monomer that has been responsible for a number of severe explosions worldwide as a result of thermal runaway. The present work was intended to lead to an improved understanding of the kinetics of the thermal polymerization and Michael addition reaction (MAR) of acrylic acid. Sealed cell differential scanning calorimetry was carried out, and the kinetics of the thermal polymerization of acrylic acid were assessed on the basis of the model-free Friedman method. In addition, microcalorimetry using a Thermal Activity Monitor IV apparatus was conducted to determine the kinetic parameters for the MAR. The rate constant for the MAR was found to be k (s−1) = 3.45 × 105 × exp (− 9.48 × 103/T (K)), while the activation energy was 78.8 kJ mol−1. The progress of the MAR was fitted with an n-order reaction model, and the reaction order as well as the rate constant was determined to be linearly proportional to temperature. By employing a modified n-order reaction model in which the reaction order was a linear function of temperature, we obtained a reaction rate equation for the MAR that closely reproduced the experimental results over a wide temperature range.

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Abbreviations

A :

Pre-exponential factor (s−1)

B :

Baseline signal for heat flow in calorimetry (W g−1)

E a :

Activation energy (kJ mol−1)

f(α):

Reaction model (–)

K :

Reaction rate constant (s−1)

N :

Reaction order (–)

R :

Gas constant (J mol−1 K−1)

S :

Heat flow signal in calorimetry (W g−1)

T :

Time (s or min or h)

t α :

Time at which the reaction progress is α (s)

T :

Temperature (°C or K)

T 0 :

Initial temperature (°C or K)

T f :

Final temperature (°C or K)

α :

Reaction progress, conversion (–)

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Acknowledgements

Part of this work was supported by JSPS KAKENHI grant number JP 20J15388, 18KT0012, and the Environment Research and Technology Development Fund (JPMEERF20191004) of the Environmental Restoration and Conservation Agency of Japan.

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Authors and Affiliations

  1. Graduate School of Environment and Information Sciences, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa, 240-8501, Japan

    Michiya Fujita & Yu-ichiro Izato

  2. Institute of Advanced Sciences, Yokohama National University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan

    Atsumi Miyake

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  1. Michiya Fujita
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  2. Yu-ichiro Izato
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  3. Atsumi Miyake
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Correspondence to Atsumi Miyake.

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Fujita, M., Izato, Yi. & Miyake, A. Kinetic analysis of the spontaneous thermal polymerization of acrylic acid. J Therm Anal Calorim 144, 435–442 (2021). https://doi.org/10.1007/s10973-020-10534-z

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  • DOI: https://doi.org/10.1007/s10973-020-10534-z

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