Effects of the surface chemical groups of cellulose nanocrystals on the vulcanization and mechanical properties of natural rubber/cellulose nanocrystals nanocomposites

Cellulose nanocrystals (CNCs), as the promising reinforcing fillers in the rubber industry, their surface chemical groups have vital effects on the vulcanization kinetics, cross-linking densities, and mechanical properties of rubber composites. Herein, CNCs with acidic carboxyl (CCA) and alkaline amino groups (CCP) were produced by modifying the sulfonic CNCs (CCS) in environment-friendly ways. Studies found the CCS and CCA with acid groups have obvious inhibiting effects on the vulcanization of natural rubber (NR), while CCP with alkaline amino groups accelerates the vulcanization of NR. Differential scanning calorimeter, Fourier transform infrared spectroscopy, and Electron paramagnetic resonance, etc. were performed to clarify the effecting mechanisms of CNCs surface groups on NR vulcanization. It was found that NR/CCS and NR/CCA nanocomposites vulcanize through radical reactions, and the surface acidic groups of CCS and CCA, i.e., hydroxyl, sulfonate, and carboxyl groups inactivate the sulfur radicals generated during vulcanization and depress the vulcanization activity. The amino groups of the polyethyleneimine of CCP promote the ring opening of sulfur (S8) or the breaking of polysulfide bonds connected to NR molecular chains to form sulfur anion with a strong nucleophilic ability, which leads to the cross-linking of NR/CCP reacts via ionic reaction mainly. The vulcanization rate and cross-linking density of NR/CCP are improved by the ionic reaction. And benefiting from the higher cross-linking density and the reinforcement of CCP, NR/CCP had the best physical and mechanical properties. Our work elucidates the mechanism of the surface chemical groups of CNCs affecting NR vulcanization and may provide ideas for the preparation of high-performance rubber composites reinforced by CNCs.