Molecular self-healing mechanisms between C60-fullerene and anthracene unveiled by Raman and two-dimensional correlation spectroscopy.

The self-healing polymer P(LMA-co-MeAMMA) crosslinked with C60-fullerene has been studied by FT-Raman spectroscopy in combination with two-dimensional (2D) correlation analysis and density functional theory calculations. To unveil the molecular changes during the self-healing process mediated by the Diels-Alder equilibrium between 10-methyl-9-anthracenyl groups and C60-fullerene different anthracene-C60-fullerene adducts have been synthesized and characterized by time-, concentration- and temperature-dependent FT-Raman measurements. The self-healing process could be monitored via the C60-fullerene vibrations at 270, 432 and 1469 cm(-1). Furthermore, the detailed analysis of the concentration-dependent FT-Raman spectra point towards the formation of anthracene-C60-fullerene adducts with an unusual high amount of anthracene bound to C60-fullerene in the polymer film, while the 2D correlation analysis of the temperature-dependent Raman spectra suggests a stepwise dissociation of anthracene-C60-fullerene adducts, which are responsible for the self-healing of the polymer.

Two-dimensional Raman correlation spectroscopy reveals molecular structural changes during temperature-induced self-healing in polymers based on the Diels-Alder reaction.

The thermally healable polymer P(LMA-co-FMA-co-MIMA) has been studied by temperature-dependent FT-Raman spectroscopy, two-dimensional Raman correlation analysis and density functional theory (DFT) calculations. To the best of our knowledge this study reports for the first time on the investigation of a self-healing polymer by means of two-dimensional correlation techniques. The synchronous correlation spectrum reveals that the spectrally overlapping C[double bond, length as m-dash]C stretching vibrations at 1501, 1575, 1585 and 1600 cm(-1) are perfect marker bands to monitor the healing process which is based on a Diels-Alder reaction of furan and maleimide. The comparison between experimental and calculated Raman spectra as well as their correlation spectra showed a good agreement between experiment and theory. The data presented within this study nicely demonstrate that Raman correlation analysis combined with a band assignment based on DFT calculations presents a powerful tool to study the healing process of self-healing polymers.