Cellulose nanocrystal-poly(oligo(ethylene glycol) methacrylate) brushes with tunable LCSTs

This paper reports on the synthesis of poly(oligoethylene glycol) methyl ether acrylate (POEGMA) grafted cellulose nanocrystals (CNCs) via surface initiated atom transfer radical polymerization (ATRP). An ATRP initiator (α-Bromoisobutyryl bromide) was covalently bonded to the surface of CNCs, followed by copolymerizing di(ethylene glycol) methyl ether methacrylate (MEO2MA) and oligoethylene glycol methyl ether methacrylate (OEGMA300) monomers from the surface using Cu(I)Br/2,2-dipyridal. Multiple POEGMA-g-CNC systems with varying MEO2MA/OEGMA300 content were synthesized, and they displayed a range of lower critical solution temperatures (LCSTs) in aqueous medium. μDSC endotherms and microstructural analysis indicated the collapse of POEGMA chains, followed by the aggregation of nanoparticles above their LCSTs. Cloud point measurements demonstrated a hysteresis in the heating and cooling of the POEGMA-g-CNC systems. It was found that the LCST of the nanoparticles could be tuned to between 23.8 to 63.8°C by adjusting the OEGMA300 content of the POEGMA brushes.