Kinetic Modeling of Ring-Opening Polymerization of Benzoxazines Using MIL-53-Al as a Potent Catalyst

Abdollah Omrani*, Zeynep Deliballi, Baris Kiskan*, Kerem Kaya, Yusuf Yagci

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)


In this study, we report the successful synthesis of a novel Al-based MOF/polybenzoxazine nanocomposite by a facile and green approach via thermally induced ring-opening polymerization (ROP). Structural and thermal characterization of the synthesized nanocomposite was accomplished using FTIR, XRD, BET and TGA, and DSC techniques, respectively. The Al-MOF showed catalytic activity in ROP and good thermal stability compared to the non-catalyzed system. The catalytic impact of MIL-53-Al on the ROP of benzoxazine is revealed by calorimetry at both isothermal and dynamic modes in detail. The Starink isoconversional analysis revealed that the MOF-catalyzed ROP proceeded faster at the reaction’s early stages, typically at α ≤ 40%. The Friedman method was also applied to the experimental data to get more insights into the mechanisms of the ROP reaction. Results indicated that both systems follow a conversion-dependent mechanism for cationic ROP of the benzoxazine. Although the complexity of the ROP of benzoxazines reduces the reliability of model fitting, the activation energy data were confirmed. Moreover, it was demonstrated that the reaction mechanism changes from the autocatalytic to the n-order regime during the reaction. An ROP mechanism is proposed at which the available AlO4(OH)2 octahedra act as active sites shifting the curing exotherms to lower temperatures.

Original languageEnglish
Pages (from-to)9673-9683
Number of pages11
JournalIndustrial and Engineering Chemistry Research
Issue number25
Publication statusPublished - 28 Jun 2023

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.


This work was supported by The Scientific and Technological Research Council of Turkey (TUBITAK) under Project no. 121C364. A.O. thanks TUBITAK for the CoCirculation2 fellowship in the framework of FP7-PEOPLE-2011-COFUND program.

FundersFunder number
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu121C364


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