A Three‐Armed Polymer with Tunable Self‐Assembly and Self‐Healing Properties Based on Benzene‐1,3,5‐tricarboxamide and Metal–Ligand Interactions

Abstract

The dynamic nature of supramolecules makes them useful in the fields of smart devices. The combination of multiple dynamic interactions in one material may bring some enhanced properties in mechanical property, self‐healing property, or recyclability. Thus, it is significantly meaningful to design new materials with multi‐dynamic bonds and clarify their bonding mechanisms. Here, a novel three‐armed polymer based on benzene‐1,3,5‐tricarboxamide (BTA) is developed and the polymer could be further complexed by metal ions to form dynamic zinc–imidazole interactions. In this system, BTA is located in the center, and the ligand‐functionalized monomer is copolymerized with n‐butyl acrylate to form three chains. This is the first time BTA is introduced to a self‐healing system to endow the polymer with assembly and self‐healing properties. The composition, chemical structure, assembly behavior, mechanical properties, and self‐healing properties of the polymer are investigated. It is revealed that the assembly behavior of the polymer depends on the BTA contents and time. The mechanical property can be easily tuned by ligand/metal ratio and is significantly adjusted by the polymer chain length and environment humidity. Long polymer chains not only contribute to good mechanical property but also promote the self‐healing process due to the effective physical entanglement.

Shape-Memory and Self-Healing Polymers Based on Dynamic Covalent Bonds and Dynamic Noncovalent Interactions: Synthesis, Mechanism, and Application

“…As a weak dynamic covalent bond, the disulfide bond can endow the materials with self-healing properties at lower temperature. − 2-HEDS is a small molecule with disulfide bonds and active hydroxyl groups at both ends. Therefore, HEDS is widely used in the preparation of self-healing polymers based on disulfide bonds. ,,− Wang et al prepared colorless and transparent PUs based on PTMEG, XDI, and HEDS. After being treated at 80 °C for 24 h, the healing efficiency of this PU reached only 37–39%.…”

“…There are some reversible covalent interactions such as the DA reaction, − acylhydrazone bond, − disulfide bond, , and alkoxyamine bond, , which can make the polymer exhibit self-healing properties. The reversible noncovalent interactions used in self-healing polymers include crystallization, , hydrogen bonds, , ionic interactions, , metal–ligand interactions, , and hydrophobic interactions …”

Columnar Aggregates of Azobenzene Stars: Exploring Intermolecular Interactions, Structure, and Stability in Atomistic Simulations

“…A widely employed and studied molecule in supramolecular chemistry is benzene-1,3,5-tricarboxamide (BTA) [13][14][15][16][17][18][19][20]. Due to its oblate shape and specific chemical structure, BTA forms columnar aggregates.…”

Preparation of Poly(thiol‐urethane) Covalent Adaptable Networks Based on Multiple‐Types Dynamic Motifs

“…[16,23,32] Among these supermolecular interactions, metal-ligand interactions offered a feasible strategy to be introduced into the polymeric materials' network, because there is no need especially synthetic modification for the backbone, as well as the metal ions used for ligand, are diverse. [33][34][35][36] What is more, tuning mechanical properties of materials are facilely achieved by changing the metal/ligand ratio. [7] The ideal ligand sulfur within thioether bond, disulfide bond, and thiourethane bond can coordinate with various metal or metal ions, including Ag + , Cu − , Cu 2+ , Au nanoparticles, and Ag nanoparticles et al [30,37,38] Some researchers utilized the silver (Ag) nanoparticles-thioether coordination to prepare thioethersilver polymer composites, which was found that the low adhesion between polymer resin and metal nanoparticles attenuated the mechanical performance of the hybrid materials.…”