Hydrogen-Bond-Mediated Polymers: Strengthening, Toughening, and Stabilizing Effects

Traditionally, the design and synthesis of polymers have centered on engineering their covalent chain or network structures. However, noncovalent interactions between polymer chains can influence the properties of polymers to a degree comparable to or even greater than their covalent structures. Therefore, shifting the focus of polymer design from covalent structure engineering to noncovalent interaction modulation represents a new paradigm for polymer innovation. This concept article summarizes our recent advances in H-bond-mediated polymers (HBMPs), fabricated by meticulously tuning the interchain/intersegment H-bonding interactions, in conjunction with rational design of the covalent polymer chain or network structures. We demonstrate that H-bond-mediated assembly provides an effective strategy to fabricate new polymers with unprecedented properties and sustainability, using commodity polymers as building blocks. Importantly, the synergy of multivalence cooperativity and dynamic nature of the H-bonding interactions in HBMPs can reconcile the intrinsic trade-off between mechanical strength and toughness of polymers, achieving both superhigh strength and superhigh toughness. Moreover, optimizing multivalence cooperativity can make the H-bonded crosslinks exhibit a covalent crosslinking effect, offering thermoset-like stability while preserving thermoplastic-like recyclability. The concept of HBMPs can be extended to noncovalent-bond-mediated systems, opening new avenues for polymer innovation and expanding the potential for creating functional and sustainable materials.