Surface modification of cellulose originated from different plant sources through TEMPO/Laccase/O2 oxidation

Abstract

An environmentally friendly 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation system using halogen-free reagents has attracted much attention. At present, cellulose nanofibers (CNFs) with a high carboxyl content can be prepared by TEMPO/laccase/O2 (TLO)- oxidation of hardwood bleached kraft pulp (HBKP) under aqueous conditions, while, the related research is still in its infancy. For example, the further applications of TLO-CNFs and the oxidation effect of the TLO system on cellulose from different sources have not been studied. In this work, cellulose from four different sources, that is, HBKP, softwood bleached kraft pulp (SBKP), bleached bagasse sulfate pulp (BBSP) and microcrystalline cellulose (MCC), was oxidized by using a TLO-oxidation system. All cellulose materials were found to be able to be oxidized successfully regardless of the source, which proved the universality of the TLO-oxidation system. Different from traditional TEMPO/NaBr/NaClO (TBN)-oxidation that introduces major carboxyl groups (0.846–1.154 mmol/g) and minor aldehyde groups (0.041–0.097 mmol/g) to cellulose, carboxyl (0.558–0.615 mmol/g) and aldehyde (0.218–0.235 mmol/g) groups can both be sufficiently introduced on the surface of TLO-oxidized cellulose. Based on the aldehyde groups introduced, the wet strength of the TLO-oxidized cellulose handsheet was greatly improved to 400% of the non-oxidized one due to the formation of hemiacetal linkages. In addition, oxidized cellulose can be isolated to homogeneous TLO-CNFs or TLO-cellulose nanocrystals (CNCs), and TLO-CNFs (CNCs) can easily be processed into films and hydrogels with high light transmittance and excellent mechanical properties. Remarkably, compared to the other TLO-CNFs, TLO-CNFs (BBSP) has higher aspect ratio with thinner width (nanofibers as thin as 2 nm can be achieved). Thus, the mechanical properties of TLO-CNFs (BBSP) assembled films and hydrogels were superior to others. These all providing significance and promising prospects for the applications of TLO-oxidation systems, meantime, the distinctive characteristics of TLO-CNFs (BBSP) were explored.