Tackifiers Regulate Interfacial Kinetics and Bonding Energy in Glycidyl Methacrylate‐Grafted Polyolefin/Aluminum Composites: A Multiscale Experimental and MD Study

Polyolefin‐metal laminates are critical for flexible electronics and battery packaging, yet they frequently suffer from weak interfacial bonding. This study investigated the adhesion mechanisms of glycidyl methacrylate‐grafted polyolefin/aluminum interfaces, focusing on the modulating effects of tackifier resin topology. A multiscale approach combining macroscopic rheological characterization and atomistic molecular dynamics (MD) simulations was employed to evaluate four hydrocarbon resins with distinct aliphatic, alicyclic, and aromatic architectures. Results demonstrated that aliphatic resins exhibited superior thermodynamic compatibility, acting as molecular lubricants that enhanced segmental diffusion. Consequently, the E1315‐modified system achieved a 246% increase in peel strength compared to neat adhesives, attributed to an optimal balance between interfacial wetting and bulk cohesion. MD simulations revealed that flexible aliphatic structures facilitated the migration of polar groups to the interface, increasing binding energy by approximately 28.6%, whereas rigid aromatic resins induced significant steric hindrance. A competitive mechanism between plasticization and steric hindrance was identified as the governing factor for interfacial enrichment. These findings establish a mechanistic framework for rationalizing resin selection to optimize adhesion in immiscible metal‐polymer composite systems.