2‑Hydroxyethylcellulose and Amphiphilic Block Polymer Conjugates Form Mechanically Tunable and Nonswellable Hydrogels

Herein, we report a family of mechanically tunable, nonswellable hydrogels that are based on a 2-hydroxyethylcellulose (HEC) scaffold grafted with amphiphilic diblock copolymers. Poly­[(oligo­(ethylene glycol)­methyl ether methacrylate]-b-poly­(methyl methacrylate) (POEGMA-b-PMMA) diblock copolymers of different compositions were created via RAFT polymerization using an alkyne terminated macro chain transfer agent (CTA). 2-Hydroxyethylcellulose (HEC) was modified with azide groups and the diblock copolymers were attached to the backbone via the copper-catalyzed click reaction to yield HEC-g-(POEGMA-b-PMMA) graft terpolymers. The resulting conjugates were soluble in DMF and able to form hydrogels upon simple solvent exchange in water. By increasing the concentration of the conjugates in DMF, the storage moduli of the hydrogels increased and the pore size in the gel decreased. After hydrogel formation, the structures were also found to be nonswellable (no macroscopic volume change upon incubation in water), which is an important feature for retaining size and mechanical integrity of the gels over time. Moreover, these materials were able to be electrospun into fibers that, upon hydration, formed fibrous hydrogel structures. The nonswellable and tunable mechanical properties of these materials imply great potential for a variety of applications such as personal care, active delivery, and tissue engineering.