Cellulose nanofiber-reinforced rubber composites prepared by TEMPO-functionalization and elastic kneading

Aqueous dispersion consisting of 2,2,6,6-tegramethylpyperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers (TEMPO-CNFs), dodecyltrimethylammonium chloride (DTMACl), and diethylene glycol (DEG) was oven-dried at 40 °C for 1 d to prepare a dried product. The soft and bulky TEMPO-CNF/DTMACl/DEG material was added to a carboxy group-containing nitrile-butadiene rubber (XNBR) followed by removal of all the DEG molecules by vacuum drying at 80 °C for 8 h. The mixture was then subjected to kneading with high shear forces using a two-roll mill at 20–30 °C (i.e., elastic kneading), followed by pressing at 170 °C for 20 min to prepare cross-linked XNBR composite sheets consisting of TEMPO-CNF and DTMACl. The XNBR composite sheet containing 9.9 vol% TEMPO-CNF had an average tensile strength, storage modulus at 23 °C, work of fracture, and elongation at break of 19 MPa, 47 MPa, 2.7 MJ/m³, and 230%, respectively, whereas those of the reference cross-linked XNBR sheet were 11 MPa, 11 MPa, 0.9 MJ/m³, and 220%, respectively. Scanning transmission electron microscopy observation revealed unique fibrillated and cluster-like structures of the TEMPO-CNF were likely responsible for the excellent mechanical and thermal properties. The proposed process is industrially viable for conventional kneading processes to prepare composite rubber sheets with good mechanical and thermal properties.