Achieving considerable shape-memory effects is a challenge for typical sea-island structured polymer blends. In this article, we successfully fabricated a novel heat-triggered shape-memory polymer (HSMP) based on ethylene–vinyl acetate copolymer/nitrile–butadiene rubber (EVA/NBR) thermoplastic vulcanizates (TPVs) via dynamic vulcanization. The influence of deformation temperature ( Td), recovery temperature ( Tr), and recovery time on the shape-memory behavior of the EVA/NBR (weight ratio = 80/20) TPV was investigated systematically. The shape-memory result of the EVA/NBR (weight ratio = 80/20) TPV demonstrated that when the Td was close to the melting temperature ( Tm) of the EVA phase (76°C), the TPV could obtain a good shape fixity ratio (>95%) and an excellent shape recovery ratio (>95%) at 100% stretch ratio. A shape-memory mechanism was proposed for this HSMP. The dynamic mechanical analysis results under temperature sweep mode showed that with increasing EVA content in TPVs, the tan δ decreased, while the storage modulus increased. The morphology observation showed that the cross-linked NBR particles were dispersed evenly in the etched surface of EVA/NBR TPV with an average diameter of approximately 2–6 μm. The longitudinal stretching surface of the EVA/NBR TPV exhibited the banding-like texture microstructure during the stretching process.
