Intrinsic Permanent Shape Reconfigurable Semicrystalline Biopolyester Thermoset

Catalyst-free, volatile organic solvent (VOC)-free synthesis of biobased cross-linked polymers is an important sustainable feature in polyesterification. To date, these polyesters have been extensively studied for their fundamental sustainability across various uses. The ultimate potential sustainability for these materials, however, is constrained to static structural parts due to their intractable rigid three-dimensional (3D) network. Here, we reveal intrinsic dynamic exchangeable bonds within this type of cross-linked semicrystalline network, poly(1,8-octanediol-co-1,12-docanedioate-co-citrate) (PODDC), enabling permanent shape reconfigurability. Annealing at slightly above melting-transition temperature (Tm) allows for shape reconfigurability up to nine times, comparable in performance to the existing bond-exchange systems. No reagents are involved from synthesis to shape reconfiguration, suggesting an exciting feature exhibited by this sustainable cross-linked material without the need for further chemical modification. We further extend this benefit of reconfigurability to enable flexible shape design in a smart shape-memory polymer (SMP), showing it as one of its potential applications. After its applications, it can undergo hydrolytic degradation. We envision that such multifaceted sustainability for the material will attract interest in environmentally friendly applications such as fabricating external part of soft robots and shape-morphing devices with reduced environmental impact.