Photocrosslinking of Polyacrylamides Using [2 + 2] Photodimerisation of Monothiomaleimides

Abstract

The [2 + 2] photocycloaddition of monothiomaleimides (MTMs) has been exploited for the photocrosslinking of polyacrylamides. Polymer scaffolds composed of dimethylacrylamide and varying amounts of d,l-homocysteine thiolactone acrylamide (5, 10, and 20 mol %) were synthesized via free-radical polymerization, whereby the latent thiol functionality was exploited to incorporate MTM motifs. Subsequent exposure to UV light (λ = 365 nm, 15 mW cm-2) triggered intermolecular crosslinking via the photodimerization of MTM side chains, thus resulting in the formation of polyacrylamide gels. The polymer scaffolds were characterized using Fourier transform infrared spectroscopy, UV-visible spectroscopy, 1H NMR spectroscopy, and size exclusion chromatography, confirming the occurrence of the [2 + 2] photocycloaddition between the MTM moieties. The mechanical and physical properties of the resulting gels containing various MTM mol % were evaluated by rheology, compression testing, and swelling experiments. In addition, scanning electron microscopy was used to characterize the xerogel morphology of 5 and 10 mol % MTM hydro- and organo-gels. The macro-porous morphology obtained for the hydrogels was attributed to phase separation due to the difference in solubility of the PDMA modified with thiolactone side chains, provided that a more homogeneous morphology was obtained when the photo-gels were prepared in DMF as the solvent.