Catalytic Role of Nanoconfinement inside MIL-125 (Ti) on the Ring-Opening Polymerization of Simple Benzoxazines

Abdollah Omrani*, Zeynep Deliballi, Kerem Kaya, Baris Kiskan*, Mert Akgun

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)


The influence of nanoscale confinement on the thermally induced ring-opening polymerization (ROP) of three different monofunctional benzoxazines (Bzs) was highlighted for the first time. The Bzs were solution-loaded or blended in/with a titanium-based metal-organic framework (MOF), i.e., MIL-125-based. The successful infiltration of the Bzs within the MOF was confirmed through comprehensive analyses using FTIR, BET, and DSC techniques. Remarkably, the nanoconfinement exhibited exceptional promotion of the Bzs ROP, resulting in a significant decrease in the onset temperature of the corresponding exotherms of as much as 127 °C for the nonsubstituted monomer. GPC traces revealed that high-molecular-weight polybenzoxazines (PBzs) were formed when fluorine-substituted Bz polymerized in the MOF-confined nanospaces. The catalytic role of nanoconfinement was further supported by analyzing the effective activation energy through the isoconversional method of Starink. ROP of the Bz-MIL-125 blend, where the effect of nanoconfinement was absent, demonstrated the catalytic role of MIL-125 with a less pronounced impact compared to the nanoconfined system.

Original languageEnglish
Pages (from-to)253-264
Number of pages12
JournalACS Applied Polymer Materials
Issue number1
Publication statusPublished - 12 Jan 2024

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.


The authors thank the Scientific and Technological Research Council of Turkey (TÜBİTAK) under the BİDEB Co-Funded Brain Circulation program with a grant no: 121C364 and Istanbul Technical University Research Fund.

FundersFunder number
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu121C364
Istanbul Teknik Üniversitesi


    • activation energy
    • Benzoxazine
    • catalysis
    • metal−organic frameworks (MOFs)
    • MIL-125(Ti)
    • nanoconfinement
    • ring-opening polymerization


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