Chemical Bonds Formed in Solid Wood by Reaction with Maleic Anhydride and Sodium Hypophosphite

The reaction of wood with maleic anhydride (MA) and sodium hypophosphite (SHP) has been identified as a viable modification method, with macroscopical properties indicating formation of cross-linking to explain the results. However, the chemical reaction between wood and the modification reagents has not been studied yet. To resolve this, the reaction was studied with solid-state ¹³C cross-polarization magic-angle-spinning (CP-MAS) and ³¹P MAS nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) to reveal the formation of bonds between wood components, MA and SHP during the treatments to explain the formation of cross-linking and the possible fixation of phosphorus in wood. XPS, solid state ¹³C and ³¹P MAS NMR revealed the maleation of wood in the absence of SHP, whilst its presence led to forming a succinic adduct observed through the C-P bond formation, as evidenced by the loss of the maleate C=C bonds at around 130 ppm and the upfield shift of the peak at 165-175 ppm, which was also significantly smoothed, as well as the increase in a peak at 26 ppm due to the reaction between the maleate group and SHP; however, the C-P-C bond could not be unambiguously rationalized from the obtained data. On the other hand, a resonance line at 16 ppm in ³¹P MAS NMR and the peaks in the XPS P 2p spectrum suggested the formation of a cross-linked structure at low concentrations of SHP, which was more likely to be phosphonate (C-P-O) than organophosphinic acid (C-P-C). The results herein provide a greater fundamental understanding of the mechanisms involved in the reaction of wood, MA and SHP, providing further scope for improved treatment systems in the future.