Bi- and tri-armed polyethylene glycol units endcapped with nitroaryl urea units have been synthesised. These endcapped polymers are able to self-assemble via complementary supramolecular interactions, specifically urea-urea and nitro-urea hydrogen bonding, to afford materials with dramatically increased mechanical and thermal properties when compared to those of the uncapped polyethylene glycol precursors. Thin films of the capped polymeric systems are able to self-repair following defect creation. Control over the mechanical and thermal characteristics (in terms of bulk viscosity) of the self-assembled networks was achieved by varying the proportion of tri-armed to bi-armed self-assembly units included in the polymer. These systems demonstrate water absorption and swelling capabilities that are also controllable by varying the ratio of the two types of unit. These physical properties have been optimised to realise a secondary pathway to puncture-repair as a result of swelling on water contact. (C) 2018 Elsevier Ltd. All rights reserved.