Work

Microstructure characterization of self-healing vitrimers via matrix assisted laser desorption/ionization (MALDI) and thermal desorption/pyrolysis direct analysis in real time (TDPy-DART) mass spectrometry (MS) techniques

Year: 2026

Type: article

Abstract: Vitrimers are a class of covalent adaptable network (CAN) polymers that combine the mechanical robustness of thermosets with the reprocessability and self-healing properties of thermoplastics. Their dynamic bond exchange reactions, often thermally activated, enable network rearrangement without loss of crosslink density, an attribute that makes them promising for sustainable, high-performance materials. In this study, we present a comprehensive analytical approach for the molecular and thermal characterization of vitrimer systems derived from bisphenol A diglycidyl ether (EPON 828) and tri-poly(cyclohexene carbonate) (tri-PCHC) using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), direct analysis in real time mass spectrometry (DART-MS), and its thermally assisted variant, thermal desorption/pyrolysis DART-MS (TDPy-DART-MS). MALDI-MS revealed the molecular weight distribution, repeat unit structure, and end group chemistry of the soluble prepolymer constituents, confirming the formation of tri-PCHC oligomers and the expected bisphenol-based ether structure of EPON 828. DART-MS enabled rapid, solvent-free identification of intact molecular ions and fragment species, providing insight into ionization and decomposition pathways of both components under ambient conditions. Extension of this method to TDPy-DART-MS allowed temperature-resolved examination of the vitrimer's thermal behavior, revealing sequential fragmentation associated with carbonate and ether bond cleavage, network rearrangement starting near the glass transition, and advanced decomposition above the degradation threshold. Together, these complementary techniques establish an efficient, high-throughput analytical platform for elucidating the chemical composition and thermal evolution of vitrimer materials. This multi-modal MS approach overcomes key limitations of conventional solid-state methods, enabling direct compositional analysis of complex, crosslinked polymer networks critical for the development of next-generation recyclable and self-healing materials.

Source: Polymer

DOI: 10.1016/j.polymer.2026.130525