Biomimetic adsorption of zwitterionic–xyloglucan block copolymers to CNF: towards tailored super-absorbing cellulose materials†
A biomimetic, facile approach to cellulose modification is the utilisation of self-adsorbing, naturally occurring biopolymers, such as the hemicellulose xyloglucan (XG). Herein, XG-block-poly(sulfobetaine methacrylate) (XG-b-PSBMA) zwitterionic block copolymers have been prepared and assessed for their ability to adsorb to cellulose, specifically cellulose nanofibrils (CNF). The polymers were synthesised using reversible addition–fragmentation chain-transfer (RAFT) polymerisation, employing an XG macromolecular RAFT agent (XG-RAFT), polymerising a sulfobetaine methacrylate (SBMA) under aqueous conditions. The incorporation of the XG block shifted the upper critical solution temperature (UCST) values to higher temperatures (20 and 30 °C) compared with the PSBMA homopolymers (17 and 22 °C) and the transition was also broadened. The adsorption of the polymers to a CNF surface was monitored using quartz crystal microbalance with dissipation monitoring (QCM-D), showing that the XG block enhanced the adsorption of the zwitterionic polymer. The formation of CNF-composite films was achieved utilising a facile vacuum filtration methodology, and the targeted compositions were confirmed by FT-IR and TGA analyses. The films exhibited high degrees of swelling in water, which were investigated at two different temperatures, 5 and 60 °C (below and above the polymer USCT values). These results highlight the advantage of using an XG block for the biomimetic modification of cellulose to form new cellulose-composite materials such as super-absorbing films.