Fully Biobased Shape Memory Material Based on Novel Cocontinuous Structure in Poly(Lactic Acid)/Natural Rubber TPVs Fabricated via Peroxide-Induced Dynamic Vulcanization and in Situ Interfacial Compatibilization

Shape memory polymers (SMPs) based on fully biobased poly­(lactide) (PLA)/natural rubber (NR) thermoplastic vulcanizates (TPVs) were fabricated via peroxide-induced dynamic vulcanization. Simultaneously, in situ reactive compatibilization was achieved by PLA molecule grafting onto NR chains. Differing from the general concept of spherical rubber particles being formed after dynamic vulcanization, the cross-linked NR was found to be a “netlike” continuous phase in the PLA matrix. This novel structure explained the surprising shape memory property of PLA/NR TPVs well (shape fixities ∼ 100%, shape recoveries > 95%, and fast recovery speed < 15 s at the switching temperature, ∼60 °C): the cross-linked NR continuous phase offers strong resilience and the PLA phase serves as the heat-control switch. We envision that the “green” raw materials and excellent shape memory properties of the dynamically vulcanized PLA/NR SMPs will open up a wide range of potential applications in intelligent medical devices

Bio-Based PLA/NR-PMMA/NR Ternary Thermoplastic Vulcanizates with Balanced Stiffness and Toughness: “Soft–Hard” Core–Shell Continuous Rubber Phase, In Situ Compatibilization, and Properties

Stiffness and toughness are two mutually exclusive attributes of polymer materials that contribute to significant improvements in impact strength, usually accompanied by a reduction in tensile strength. In this study, ternary thermoplastic vulcanizates (TPVs) consisting of poly­(lactic acid) (PLA), poly­(methyl methacrylate)-grafted natural rubber (NR-PMMA), and natural rubber (NR) with balanced stiffness and toughness were successfully prepared via peroxide-induced dynamic vulcanization. With 10 wt% of NR and NR-PMMA, the PLA/NR-PMMA/NR ternary TPV displayed an enhanced yield stress of 41.7 MPa (only 38% loss compared to neat PLA) and a significantly higher impact strength of 91.30 kJ/m² (nearly 32 times that of neat PLA). The in situ compatibilization between PLA and rubber phases was confirmed by Fourier transform infrared spectroscopy. Interfacial, rheological, and calorimetric measurements confirmed that the NR was encapsulated by NR-PMMA in the PLA phase. It was found that the flexibility of the “soft” NR core and outer “hard” NR-PMMA shell with excellent PLA/rubber interfacial adhesion are responsible for the super toughness and considerable tensile strength of the PLA/NR-PMMA/NR ternary TPVs