A CP/MAS ¹³C-NMR study of cellulose fibril aggregation in eucalyptus dissolving pulps during drying and the correlation between aggregate dimensions and chemical reactivity

Abstract

Changes in supramolecular properties of cellulose I, namely its lateral fibril aggregate dimension (LFAD), in bleached hardwood acid bisulphite pulp during drying was studied using cross-polarization/magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS ¹³C-NMR) in combination with spectral fitting. A significant change in aggregate dimensions was noticed when each of the pulp grades were oven dried. The effect of drying was further investigated with pulp samples subjected to different drying methods. A comparison of a harsh oven drying, mild and rapid air drying, and a very mild and slow condition drying showed that the LFAD of the material decreases in the following order: oven drying > air drying > condition drying. The correlation between the total extractable material S₁₀ (%) and LFAD and also the LFAD increment (ΔLFAD in %) are presented and shown to be intimately related. This means that the method of drying influences the size of the fibril aggregate dimensions and depends on the presence of extractable material within the fibre cell wall. Reactivity studies were carried out based on the acetylation of cotton linters and commercial 96α pulp. Results indicate that the initial reaction rate is proportional to the specific surface area of the two cellulose pulp samples. Accordingly, the specific surface area is directly related to initial reactivity of the performed acetylation. We demonstrated that it is possible to control the LFAD and hence specific surface area in laboratory-produced pulps 91α, 92α, and 96α by the drying method. Thus controlling LFAD can probably be one viable route for controlling the initial reactivity of dissolving pulp towards acetylation.