Shape memory polymers (SMPs)are widely used owing to their ability to change shapes under external stimuli. Conventional covalently crosslinked SMPs have limitations in biomedical applications. This article presents a linear shape memory biodegradable polyester without chemical crosslinks or multiblock structures. A new programming protocol is developed to split the crystals into two parts with different melting transitions through partial melting/recrystallization. The split crystals play different roles in fixation and recovery process to complete a shape memory cycle. The ratio between the partitioned crystals affects the fixed rate and recovery rate. The shape memory performance can be optimized by controlling the partial melting temperature and pre‐stretching of the sample. Examples of complicated shape changes demonstrate the effectiveness of the proposed technique. The method is applicable to crystallizable linear polymers and has potential applications in implantation devices.
The development of artificial organs and implants demands new materials with both processability and functionality. A series of star like poly(CL-co-TOSUO) copolymers with different molecular weights are synthesized via ring-opening polymerization. The polymers are modified with norbornene end groups for rapid photo-crosslinking. Due to the random insertion of 1,4,8-trioxaspiro-[4,6]-9-undecanone and well-constructed permanent chemical network, the photocrosslinked elastomers are more flexible and resilient than conventional poly (ε-caprolactone), with 84% resilience above the melting point. Their thermal and mechanical properties can be fine-tuned by varying the molecular weights of the precursors. The polymer can be fabricated into complex shapes by digital light processing 3D printing. Combined with good cytocompatibility and degradability, the highly flexible elastomers show great potential for tissue engineering.
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