Maintaining the structural integrity of solid rocket propellant charges has been widely concerned by scholars around the world. The introduction of a polyester transition layer between the propellant and the liner is a new and effective method used to improve the interfacial bonding properties of the solid propellant charge and inhibit the migration of high-energy plasticizers. Uniaxial tensile pull-off specimens and accelerated aging experiments at multiple temperatures were used to study the interfacial bonding properties of propellant charges and the migration properties of plasticizers, respectively. The influence of the polyester structure on the two properties was also discussed in detail, and a targeted antimigration mechanism was proposed based on the molecular structure of the plasticizer. In addition, the Weibull model was used to fit the plasticizer migration behavior, and the plasticizer migration master curve in the charge system was obtained based on the principle of time–temperature superposition, which broadens the application field of the model and is important from an application perspective.