Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds.

Despite numerous strategies involving dynamic covalent bond exchange for dynamic and self-healing materials, it remains a challenge to be able to tune the malleability and self-healing properties of bulk materials through simple small molecule perturbations. Here we describe the use of tunable rates of boronic ester transesterification to tune the malleability and self-healing efficiencies of bulk materials. Specifically, we used two telechelic diboronic ester small molecules with variable transesterification kinetics to dynamically cross-link 1,2-diol-containing polymer backbones. The sample cross-linked with fast-exchanging diboronic ester showed enhanced malleability and accelerated healing compared to the slow-exchanging variant under the same conditions. Our report demonstrates the possibility of transferring small molecule kinetics to dynamic properties of bulk solid material and may serve as a guide for the rational design of tunable dynamic materials.

Self-healing multiphase polymers via dynamic metal-ligand interactions.

A new self-healing multiphase polymer is developed in which a pervasive network of dynamic metal-ligand (zinc-imidazole) interactions are programmed in the soft matrix of a hard/soft two-phase brush copolymer system. The mechanical and dynamic properties of the materials can be tuned by varying a number of molecular parameters (e.g., backbone/brush degree of polymerization and brush density) as well as the ligand/metal ratio. Following mechanical damage, these thermoplastic elastomers show excellent self-healing ability under ambient conditions without any intervention.

Mechanically Robust and Self-Healable Superlattice Nanocomposites by Self-Assembly of Single-Component "Sticky" Polymer-Grafted Nanoparticles.

A simple, scalable synthesis of mechanically robust and self-healable superlattice nanocomposites is achieved through self-assembly of single-component "sticky" polymer-grafted nanoparticles. The multi-valent hydrogen-bonding interactions between the nanoparticles provide strong cohesive energy, binding the nanoparticles into strong and tough materials. Furthermore, the dynamic hydrogen-bonding interactions afford the formation of highly dynamic, self-healing, and mechanochromic nanocomposite materials in the bulk.