Mechanically robust supramolecular polymer co-assemblies

Abstract

Supramolecular polymers are formed through non-covalent, directional interactions between monomeric building blocks. The assembly of these materials is reversible, which enables functions such as healing, repair, or recycling. However, supramolecular polymers generally fail to match the mechanical properties of conventional commodity plastics. Here we demonstrate how strong, stiff, tough, and healable materials can be accessed through the combination of two metallosupramolecular polymers with complementary mechanical properties that feature the same metal-ligand complex as binding motif. Co-assembly yields materials with micro-phase separated hard and soft domains and the mechanical properties can be tailored by simply varying the ratio of the two constituents. On account of toughening and physical cross-linking effects, this approach affords materials that display higher strength, toughness, or failure strain than either metallosupramolecular polymer alone. The possibility to combine supramolecular building blocks in any ratio further permits access to compositionally graded objects with a spatially modulated mechanical behavior.

Plasticization of a Semicrystalline Metallosupramolecular Polymer Network

“…Moreover, a comparison of the first DSC heating traces of compressionmolded and solvent-cast samples shows a minor increase in the T m for the former, which is most pronounced for TAB:Zn_5% samples (Figures S5 and S6; Table S1). This observation is tentatively interpreted as an annealing effect, as previously observed for neat TAB:Zn, 42 and corroborated by the fact that the first cooling and second heating traces of melt-processed samples mirror those of solvent-cast samples (Figures S5 and S6). The DSC measurements, hence, indicate that the semicrystalline nature of the MSP network is retained in the presence of the plasticizer, even though the melting and crystallization temperatures are slightly lower if the DIDP content is above 5 wt %.…”

Metallosupramolecular polymers as precursors for platinum nanocomposites

“…Irradiated samples, hence, feature nanostructures that are larger than those observed after thermal treatment at temperatures of 200 °C, perhaps, because the intense UV light leads to an increased heating rate and higher temperatures are reached upon prolonged exposure. 33,46,47…”

“…Irradiated samples, hence, feature nanostructures that are larger than those observed after thermal treatment at temperatures of 200 °C, perhaps, because the intense UV light leads to an increased heating rate and higher temperatures are reached upon prolonged exposure. 33,46,47 The irradiation of samples with UV light through a photolithography mask was used to create patterned nanocomposites. After casting solutions of P1 (c = 0.5 mol L -1 ) onto quartz glass substrates followed by drying in ambient atmosphere overnight, the samples were exposed to UV irradiation (15 min; 320-360 nm; 900 mW cm -2 ) using a photomask (Fig.…”

Experimental Comparison of Bond Lifetime and Viscoelastic Relaxation in Transient Networks with Well-Controlled Structures

“…In contrast, transient networks cross-linked by temporary interactions, including wormlike micelles − and associative polymers, − exhibit characteristic viscoelasticity with a single relaxation mode, despite being polymeric liquids. These temporal characteristics have been widely utilized in self-healing − and robust soft materials. − Owing to their simplicity, the transient networks have attracted considerable interest as model systems for viscoelastic liquids.…”