Self‐Healable and Tough Thermoplastic Materials from Metal–Thioether Block Polymers

Abstract

Thioether‐based acrylate block polymers are conveniently prepared via reversible addition–fragmentation chain‐transfer polymerization, and further combined with the merit of reversible metal–thioether coordination to fabricate a new type of “smart” thermoplastic materials. This metal/polymer hybrid architecture imparts extraordinary mechanical performance to the product materials, exhibiting an excellent ductility (breaking strain ≈ 1000%) as well as a relatively high breaking stress (1–5 MPa). Notably, it is facile to thermally process these materials into desired shapes (e.g., dog‐bone specimens, films, disks, etc.). Most importantly, these thermoplastic materials are endowed with the smart characteristic of being self‐healable under ambient conditions. To the authors' knowledge, it is the first report on thermally processable, self‐healing, and mechanically tough thermoplastic materials based on thioether polymers. These discoveries not only provide a pioneering route to design and construct self‐healing thermoplastics, but also elucidate the pathway toward a large portfolio of new hybrid materials built on the platform of organosulfur chemistry.

Mechanical and Structural Consequences of Associative Dynamic Cross-Linking in Acrylic Diblock Copolymers

“…there are several studies in which phase-separating block copolymers were cross-linked by H-bonds, 4,5 hindered urea dynamic covalent bonds, 77 or metal-ligand complexation. 6,7,[78][79][80] In these examples, the cross-linked networks generally exhibit a single broad SAXS peak, consistent with disorganized phaseseparated morphologies; corresponding transmission electron micrographs (TEMs), when available, reveal micellar or bicontinuous morphologies. 6,7,77 Interestingly, Noro and Matsushita could regain long-range order in their H-bonded block copolymer networks by adding a salt that interacted selectively with one block, raising the effective interaction parameter.…”

“…Permanently cross-linking a block copolymer in the disordered state, either in a melt above T ODT or in a good solvent, can permit or prevent reorganization of the resulting network depending on cross-link density. Lightly cross-linked block copolymer networks reassemble into organized morphologies upon cooling or solvent removal, but over a critical cross-link density, the networks are trapped in a disordered or disordered-like state. − Dynamic cross-links can also interfere with long-range order; there are several studies in which phase-separating block copolymers were cross-linked by H-bonds, , hindered urea dynamic covalent bonds, or metal–ligand complexation. ,,− In these examples, the cross-linked networks generally exhibit a single broad SAXS peak, consistent with disorganized phase-separated morphologies; corresponding transmission electron micrographs (TEMs), when available, reveal micellar or bicontinuous morphologies. ,, Interestingly, Noro and Matsushita could regain long-range order in their H-bonded block copolymer networks by adding a salt that interacted selectively with one block, raising the effective interaction parameter . However, the kinetic barriers to reorganizing the H-bonded network are significantly lower than the barriers to reconfiguration in a vitrimer.…”

Mechanical and structural consequences of associative dynamic cross-linking in acrylic diblock copolymers

“…[73][74][75][76] Dynamic cross-links can also interfere with long-range order; there are several studies in which phase-separating block copolymers were cross-linked by H-bonds, 4,5 hindered urea dynamic covalent bonds, 77 or metal-ligand complexation. 6,7,[78][79][80] In these examples, the cross-linked networks generally exhibit a single broad SAXS peak, consistent with disorganized phaseseparated morphologies; corresponding transmission electron micrographs (TEMs), when available, reveal micellar or bicontinuous morphologies. 6,7,77 Interestingly, Noro and Matsushita could regain long-range order in their H-bonded block copolymer networks by adding a salt that interacted selectively with one block, raising the effective interaction parameter.…”

Synthesis and Properties of Networks Based on Thiol‐ene Chemistry Using a CO2‐Based δ‐Lactone

“…Thioethers have good metal complexation ability, and many researchers have utilized the merit to construct elastomers, chelating resins, self‐healable materials, and nanoparticles . Thioether is an intrinsic part of TEN, and we investigated the complexation properties of the networks with Cu 2+ , Ni 2+ , Fe 3+ , and Co 2+ .…”