Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of non- covalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on p-electron-rich pyrenyl residues and p-electron-deficient, chain-folding aromatic diimides that interact through complementary p–p stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials

Catalytic Control of the Vitrimer Glass Transition

Vitrimers, strong organic glass formers, are covalent networks that are able to change their topology through thermoactivated bond exchange reactions. At high temperatures, vitrimers can flow and behave like viscoelastic liquids. At low temperatures, exchange reactions are very long and vitrimers behave like classical thermosets. The transition from the liquid to the solid is reversible and is, in fact, a glass transition. By changing the content and nature of the catalyst, we can tune the transesterification reaction rate and show that the vitrimer glass transition temperature and the broadness of the transition can be controlled at will in epoxy-based vitrimers. This opens new possibilities in practical applications of thermosets such as healing or convenient processability in a wide temperature range

Solvent-assisted programming of flat polymer sheets into reconfigurable and self-healing 3D structures

It is extremely challenging, yet critically desirable to convert 2D plastic films into 3D structures without any assisting equipment. Taking the advantage of solvent-induced bond-exchange reaction and elastic-plastic transition, shape programming of flat vitrimer polymer sheets offers a new way to obtain 3D structures or topologies, which are hard for traditional molding to achieve. Here we show that such programming can be achieved with a pipette, a hair dryer, and a bottle of solvent. The polymer used here is very similar to the commercial epoxy, except that a small percentage of a specific catalyst is involved to facilitate the bond-exchange reaction. The programmed 3D structures can later be erased, reprogrammed, welded with others, and healed again and again, using the same solvent-assisted technique. The 3D structures can also be recycled by hot-pressing into new sheets, which can still be repeatedly programmed