Rigid‐Flexible Coupled Dendritic Molecule Doping: General Approach to Activate Commercial Polymers into Harsh Condition‐Tolerant Multi‐Reusable Strong Supramolecular Adhesives.

Developing functional adhesives combining strong adhesion, good recyclability and diverse harsh‐condition adaptability is a grand challenge. Here, we introduce a general dendritic molecule doping strategy to activate commercial polymers into a new family of supramolecular adhesives integrating high adhesion strength, ultralow temperature, water resistant and multi‐reusable properties. Our method involves rational design of a new rigid‐flexible coupled dendritic molecule—M4C8OH as a versatile dopant, while simple M4C8OH doping into commercial polymers can modulate internal and external non‐covalent interaction to enable H‐bonding enhanced interchain cross‐linking for tough cohesion along with enhanced interphase interaction. This endows 20 wt % M4C8OH‐doped polycaprolactone (PCL) adhesives (PCL‐M4C8OH) with improved adhesion strength on various substrates with the maximum increase up to 2.87 times that of PCL. In particular, the adhesion strengths of PCL‐M4C8OH on polymethyl methacrylate at 25 °C and −196 °C reach 4.67 and 3.58 MPa—1.9 and 2.3 times those of PCL and superior to diverse commercial adhesives and most reported adhesives. PCL‐M4C8OH also displays markedly‐improved multi‐usability and tolerance against ultralow temperature and diverse wet environments. Mechanism studies reveal the crucial role of M4C8OH molecular structures toward superior adhesion. Our method can be expanded to other polymer matrices, yielding diverse new supramolecular adhesives. [ABSTRACT FROM AUTHOR]