Design and Synthesis of Quick Setting Nonswelling Hydrogels via Brush Polymers

Brush polymers have emerged as components of novel materials that show huge potential in multiple disciplines and applications, including self‐assembling photonic crystals, drug delivery vectors, biomimetic lubricants, and ultrasoft elastomers. However, an understanding of how this unique topology can affect the properties of highly solvated materials like hydrogels remain under investigated. Here, it is investigated how the high functionality and large overall size of brush polymers enhances the gelation kinetics of low polymer weight percent gels, enabling 100‐fold faster gelation rates and 15‐fold higher stiffness values than gels crosslinked by traditional star polymers of the same composition and polymer chain length. This work demonstrates that brush polymer topology provides a useful means to control gelation kinetics without the need to manipulate polymer composition or crosslinking chemistry. The unique architecture of brush polymers also results in restrained or even nonswelling behavior at different temperatures, regardless of the polymer concentration. Brush polymers therefore are an interesting tool for examining how high‐functionality polymer building blocks can affect structure–property relationships and chemical kinetics in hydrogel materials, and also provide a useful rapidly‐setting hydrogel platform with tunable properties and great potential for multiple material applications.