ABSTRACT
Biopolymers, especially cellulose, are vital to transitioning to a circular economy and reducing our reliance on fossil fuels. However, for many applications a high degree of cellulose hydroxyl modification is necessary. The challenge is that the chemical features of the hydroxyls of cellulose and water are similar. Therefore, chemical modification of cellulose is often explored under non-aqueous conditions with systems that result in high hydroxyl accessibility and reduce cellulose aggregation. Unfortunately, these systems depend on hazardous and complex solvents from fossil resources, which diverge from the initial sustainability objectives. To address this, we developed three new betaine-based ionic liquids that are fully bio-based, scalable, and green. We found that a specific ionic liquid had the perfect chemical features for the chemical activation of cellulose without disturbing its crystalline ordering. The high activation in heterogeneous conditions was exemplified by reacting cellulose with succinic anhydride, resulting in more than 30 % conversion of all hydroxyls on cellulose. Overall, this work opens new perspectives for the derivatization of cellulosic materials while simultaneously "keeping it green".
ABSTRACT
We report the synthesis of networks having adjustable topologies and mechanical properties. Our approach consists of photopolymerizing poly(ethylene glycol) diacrylates (PEG-DA) in the presence of mixtures of mono- and multifunctional thiols. We show that the introduction of monothiols as non-cross-linking transfer agents provides a simple way to tune the topology of the networks and produce soft extensible networks. In a systematic study with model short PEG-DA (Mn = 700 g·mol-1), we explored how the gel point and network properties, such as the swelling ratio, the soluble fraction, the viscoelastic moduli, and the ultimate stress and strain, can be adjusted by varying the ratio of thiol to acrylate functions and the average functionality of the thiol mixture. We applied this strategy to longer chains of PEG-DA (Mn = 2300 and 3200 g·mol-1) and varied the viscoelastic and tensile responses of these networks to optimize their adhesive performance. This simple and robust approach further enriches the toolbox of thiol-acrylate polymerization and expands the application scope of PEG-based hydrogels.
