A Polymer System with Ultra‐High Molecular Potential Energy

Abstract In contrast to small molecules, macromolecules exhibit distinctive characteristics due to their higher potential energy ( E P ). These include elevated viscosity, enhanced tensile strength, cohesiveness, and stability. The E P of macromolecules can be modulated through the design of side groups, but this approach may also alter chemical properties. This study introduces an α‐methylation strategy that significantly enhances E P without modifying the structure of these side groups. This increase in E P induces a transition in the rheological behavior of polymer systems from a rubbery to a glassy state. Concurrently, it improves hygrothermal tolerance without changing dynamic bond groups. The application of this ultra‐high E P strategy results in substantial enhancements in traditional acrylic adhesives: a 1500% increase in adhesion strength and a 33200% rise in adhesion modulus when exposed to hot water. Polymer is endowed with a shape memory function due to ultra‐high E P . With the dual interface locking of this function, the adhesion strength can be increased by 70%. This ultra‐high E P strategy provides a possible explanation for the origin of vitrification in polymeric systems.