The
challenge of hitherto elaborating a workable approach to overcome
the conflicts between stiffness, ductility, and transparency of polystyrene
(PS) still remains among academia and industry. In this work, we found
an unprecedented strategy to address this obstacle by combining mechanical
and thermal rejuvenation. A PS film with remarkable stiffness, ductility,
and transparency (83.1 MPa, 87.9, and 83.1%) is achieved through this
facile strategy. Through investigating the relationship between macroscopical
mechanical performance and mobility of molecular chains, the mechanism
of the coupling effect is elucidated. On heating up the mechanically
rejuvenated films, the intersegmental interaction is weakened and
external pressure breaks the force balance. Thus, the oriented chain
network might be more inclined to form a densely arranged structure,
and it provides more strengthened elements during yielding. This work
provides a preferable and industrially scalable method to prepare
high-performance PS materials and might be a significant guidance
for other amorphous polymers.