Synthesis and characterization of ureidopyrimidinone-functionalized polyurethane acrylates and their hybrid nanocomposites for UV coating applications

Abstract

In this study, ureidopyrimidinone moieties (UPy), capable of physical crosslinking via quadruple hydrogen bonding, were successfully incorporated into UV-curable polyurethane acrylate prepolymers. First, a hydroxyl-terminated unsaturated ester monomer was synthesized and reacted with isophorone diisocyanate to create a hydroxyl-terminated UV-curable urethane oligomer (U–OH). Then, isocyanate-terminated building blocks (UPy moieties and an acrylate-based photosensitive monomer) were synthesized and used in various ratios to functionalize U–OH for the preparation of a series of UV-curable UPy-containing polyurethane acrylate (PUA) resins. The resulting products were structurally characterized using 1H NMR and FTIR spectroscopy. Furthermore, organic–inorganic hybrid nanocomposites were obtained by introducing silane coupling agents into PUA resins using the sol–gel process. A series of UV-curable UPy-containing PUA coatings and hybrid nanocomposites were prepared, and their synergistic effect on coating properties was investigated. The dynamic mechanical analysis revealed that the Tg of the samples increased with increasing UPy content, although the mechanical properties remained largely unaltered, as shown by the stress–strain test. The studies also demonstrated that the hybrid nanocomposites exhibited higher decomposition temperatures and better thermal stability compared to pure PUAs. All the coatings exhibited good transparency in the visible region. An optical microscope was used to investigate the self-healing property by scratching the plexiglass panels with a razor blade. Among the other samples, the coating with the highest percentage of UPy content exhibited the best self-healing ability after heat treatment at 90 °C for 10 min. Graphical abstract