Impact of Aqueous Grafting of Polystyrene through Methacrylate-Modified Cellulose Nanofibrils on Emulsion Stabilization and Drying Behavior

Cellulose nanofibrils (CNFs) are abundant materials limited in application by their hydrophilic nature and fibrillar collapse during drying. Herein, hydrophobic CNFs (PS-MetCNFs) were produced via the grafting of polystyrene through a methacrylate handle on modified CNFs. This modification prevented fibrillar collapse of the CNFs upon drying with as low as 3.5 wt % polystyrene. System characterization through kinetics studies and controls revealed that a surfactant-free emulsion polymerization ran parallel to the grafting-through polymerization. Polystyrene on the PS-MetCNFs was both covalently bound and noncovalently bound. This noncovalently bound polymer was due to polymerization in the monomer-swollen polymer particles on the PS-MetCNF surface. The polystyrene modification interfered with CNF Pickering emulsion behavior, instead stabilizing monomer-swollen polymer particles entangled in the CNF network. Composites of PS-MetCNFs and poly(lactic acid) showed higher maximum tensile stress and modulus at 5 wt % loading relative to composites made with unmodified spray-dried CNFs, demonstrating a route to composite reinforcement with CNFs without energy-intensive spray drying.