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Effect of ethylbenzene proportion on thermal behavior in styrene polymerization: kinetics and the glass transition temperature

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Abstract

A rapid increase in viscosity during the polymerization process impacts the polymerization rate. To address this issue, ethylbenzene is often introduced into the polymerization system in order to reduce viscosity. The thermal characteristics of styrene–ethylbenzene polymerization have been identified using differential scanning calorimetry. The rate of heat generation significantly decreases as the proportion of ethylbenzene increases. The polymerization product mixtures were analyzed using gel permeation chromatography. Polymerization at low viscosity yields a higher proportion of low molecular mass polymers and a more uniform distribution of product chain lengths compared to polymerization at high viscosities. The glass transition temperature and the activation energy for viscous flow of the products were also determined. The apparent kinetics of styrene polymerization may be described using the “autocatalytic + Nth-order” model. Two stages of monomer conversion are apparent: polymerization reactions initiated by AIBN and thermally induced polymerization. Valuable insights into the polymerization process which can contribute to the optimization of industrial polymerization reactions have been obtained.

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Abbreviations

A :

Frequency factor (s−1)

C p :

Specific heat capacity (J g−1 K−1)

c :

Polymer concentration (mol L−1)

D :

The distribution coefficient

E :

The apparent activation energy of reaction (kJ mol−1)

E a :

The apparent activation energy of viscous flow (kJ mol−1)

f :

The free volume fraction

M n :

Number-average molecular mass (g mol−1)

M w :

Mass-average molar mass (g mol−1)

n :

Order of reaction

q :

Heat flow(mW)

t :

Time (s)

T :

Temperature (℃)

T i :

The initial polymerization temperature (℃)

T f :

The final polymerization temperature (℃)

T g :

Glass transition temperature (℃)

α :

Fraction of monomer conversion

v f :

Volume expansion coefficient

V :

The total volume

V 0 :

The occupied volume

\( \eta \) :

Viscosity (Pa s−1)

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Acknowledgements

The authors thank the National Natural Science Foundation of China (22278226) and Postgraduate Research Practice Innovation Program of Jiangsu Province (KYCX-23_0417).

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Authors and Affiliations

  1. Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, Jiangsu, China

    Huanhuan Chen, Chenghui Fang, WenQian Wu, Shichun Weng, Liping Chen, Zichao Guo & Wanghua Chen

  2. China Safety Technology Research Academy of Ordnance Industry, Beijing, 100053, China

    Juan Zhou

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Contributions

HC was contributed conceptualization, methodology, visualization, data curation, and writing–original draft; CF was analyzed experiments and data analysis; JZ was responsible for methodology and software; WW analyzed methodology; SW performed experimental design; LC was done revision; ZG did validation; and Wanghua Chen was involved in resources and supervision.

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Correspondence to Liping Chen.

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The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.

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Chen, H., Fang, C., Zhou, J. et al. Effect of ethylbenzene proportion on thermal behavior in styrene polymerization: kinetics and the glass transition temperature. J Therm Anal Calorim 149, 2929–2940 (2024). https://doi.org/10.1007/s10973-023-12876-w

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