Cellulose Nanocrystals Grafted with Polystyrene Chains through Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP)

This paper reports the synthesis of cellulose nanocrystals grafted by polystyrene chains via surface-initiated ATRP. Naturally occurring cellulose was first hydrolyzed to obtain cellulose nanocrystals. Their surface was then chemically modified using 2-bromoisobutyryl bromide to introduce initiating sites for ATRP. A varying extent of surface modification was achieved by changing reaction conditions. Further initiation of styrene polymerization from these modified nanocrystals with a CuBr/PMDETA (N,N,N′,N′,N′′-pentamethyldiethylenetriamine) catalytic system and in the presence of a sacrificial initiator produced polysaccharide nanocrystals grafted by polystyrene chains. A range of nanocrystals-g-polystyrene with different graft lengths (theoretical polymerization degree = 27−171) was synthesized through this method and characterized by elemental analysis, XPS, FT-IR, TEM, and contact angle measurements. We are thus able to produce cellulose nanoparticles with varying grafting densities (by altering extent of initiator surface modification) and varying polymer brush length (through polymerization control). The nanocrystals-g-polystyrene (NC-g-PS) particles were tested for their capacity to absorb 1,2,4-trichlorobenzene from water. The results obtained show that they can absorb the equivalent of 50% of their weight in pollutant compared to 30 wt % adsorption for nonmodified nanocrystals, while also displaying faster absorption kinetics.