On the Para/Ortho Reactivity of Isocyanate Groups during the Carbamation of Cellulose Nanocrystals Using 2,4-Toluene Diisocyanate

Abstract

2,4-toluene diisocyanate (TDI) has been commonly used to bind molecules and polymers onto the surface of cellulose nanocrystals (CNCs). Such a process usually involves two steps: (1) the more reactive para-isocyanates (p-NCOs) of TDI are reacted with the surface hydroxyl groups of CNCs then (2) the ortho-isocyanates (o-NCOs) are reacted with certain desired molecules. During the first reaction, an ideal para/ortho selectivity could be impossible to achieve, as o-NCOs are not fully unreactive. Therefore, there is a need to better understand the reaction between CNCs and TDI towards a maximum para/ortho selectivity. For that goal, CNCs were reacted with TDI under varying temperatures (35–75 °C) and TDI/CNCs molar ratios (1–5). The amount of the reacted TDI was estimated using elemental analysis while the free o-NCO groups were quantified following the hydrolysis method of Abushammala. The results showed that temperature had a negative impact on para/ortho selectivity while TDI/CNCs molar ratio improved it. A maximum selectivity of 93% was achieved using a temperature of 35 °C and a molar ratio of 3. This is a three-fold improvement to that using the traditional reaction conditions (75 °C and molar ratio of 1).