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Cationic Photopolymerization of Biobased Oxetane Monomers Obtained from Adipic, Itaconic, and Citric Acid Functionalization
Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-7790-8987
Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy.ORCID iD: 0000-0002-8630-1802
2025 (English)In: Macromolecular Chemistry and Physics, ISSN 1022-1352, E-ISSN 1521-3935, Vol. 226, no 21, article id e00233Article in journal (Refereed) Published
Abstract [en]

Cationic photopolymerization offers a significant advantage over radical polymerization due to its resistance to oxygen inhibition and superior dimensional stability during the crosslinking process. In this study, we aim to advance the development of bio-based monomers for cationic photopolymerization by synthesizing oxetane-functionalized derivatives of adipic, itaconic, and citric acids. These three renewable acids were chosen for their multifunctionality and availability. The synthesized monomers, bis((3-methyloxetan-3-yl)methyl) adipate (BOA), bis((3-methyloxetane-3-yl)methyl) itaconate (BOI), and tris((3-methyloxetane-3-yl)methyl) citrate (TOC), were fully characterized using nuclear magnetic resonance (NMR). Fourier transform infrared (FTIR) spectroscopy and photo differential scanning calorimetry (photo-DSC) were employed to monitor the oxetane ring-opening reaction kinetics and to determine the degree of conversion, revealing high reactivity in all monomers, reaching nearly complete conversion within 90 s. The mechanical properties of the UV-cured films were assessed by dynamic mechanical thermal analysis (DMTA) and gel content measurements. Results indicated that the BOI-based films exhibited higher glass transition temperatures (Tg) and crosslinking densities compared to BOA- and TOC-based films. The findings demonstrate the potential of bio-based oxetane monomers to produce UV-curable materials with acceptable thermomechanical properties, offering a sustainable alternative to petroleum-derived precursors.

Place, publisher, year, edition, pages
Wiley , 2025. Vol. 226, no 21, article id e00233
Keywords [en]
adipic acid, bio-based, cationic photopolymerization, citric acid, itaconic acid, oxetane, UV-curing
National Category
Polymer Chemistry Polymer Technologies Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-369931DOI: 10.1002/macp.202500233ISI: 001551212300001Scopus ID: 2-s2.0-105013458713OAI: oai:DiVA.org:kth-369931DiVA, id: diva2:1998985
Note

QC 20260119

Available from: 2025-09-18 Created: 2025-09-18 Last updated: 2026-01-19Bibliographically approved

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Papadopoulos, LazarosHakkarainen, Minna

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