Surface Modification of Cellulose Nanocrystals via RAFT Polymerization of CO2-Responsive Monomer-Tuning Hydrophobicity.
Joaquin ArredondoNicole M WoodcockOmar Garcia-ValdezPhilip G JessopPascale ChampagneMichael F CunninghamPublished in: Langmuir : the ACS journal of surfaces and colloids (2020)
Cellulose nanocrystals (CNCs) were converted into a CO2-responsive composite nanomaterial by grafting poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(diethylaminoethyl methacrylate) (PDEAEMA), and poly(diisopropylaminoethyl methacrylate) (PDPAEMA) onto its surface using both grafting-to and grafting-from approaches. The zeta potential (ζ) of the graft-modified CNC could be reversibly switched by protonation/deprotonation of the tertiary amine groups simply by sparging with CO2 and N2, respectively. Depending on the grafting density and the molecular weight of the polymer grafts, CNC can form stable aqueous dispersions at either mildly acidic pH (under CO2) or mildly basic (under N2) conditions. Moreover, it was also determined that the CNC hydrophobicity, assessed using phase-shuttling experiments at different pH values, was also dependent on both the grafting density and molecular weight of the polymer grafts, thereby making it possible to easily tune CNC dispersibility and/or hydrophobicity.