Rapid Synthesis of Self‐Healing, <scp>pH</scp>‐Responsive <scp>IA</scp>‐Based Hydrogels via Frontal Polymerization

ABSTRACT Self‐healing polymeric gels have emerged as a promising class of materials due to their ability to repair damage autonomously, offering significant advantages for various applications. Nevertheless, a major hurdle to their widespread practical use lies in their often‐compromised mechanical strength and long reaction time. Herein, we present the synthesis of a new type of self‐healing hydrogels using poly(itaconic acid‐co‐hydroxypropyl alcohol‐co‐acrylic acid), also known as poly(IA‐co‐HPA‐co‐AAc), by a frontal polymerization (FP) method. The rapid reaction rate of FP facilitates the swift and energy‐efficient synthesis of the hydrogels within 10 min, eliminating the need for prolonged reaction times. Additionally, the results revealed that the synthesized hydrogels exhibited pH‐dependent responsiveness, robust mechanical integrity, and autonomous self‐healing capabilities, obviating the requirement for external stimuli. The exceptional self‐healing properties can be attributed to the extensive hydrogen bonding network between the polymer chains, enabling them to recover up to 80% of their original mechanical strength. Rheological analysis confirmed the presence of a robust and stable gel network, evidenced by high storage modulus ( G ′) values across the entire frequency and strain sweep tests. This research addresses a significant knowledge gap in IA‐based hydrogels by introducing a rapid, optimized method for constructing self‐healing materials through hydrogen bonding interactions.