Perylene as an electron-rich moiety in healable, complementary π–π stacked, supramolecular polymer systems

Abstract

a b s t r a c tA two-component, supramolecular polymer blend has been designed using a novel p-electron rich bisperylene-terminated polyether. This polymer is able to self-assemble through electronically complementary pep stacking interactions with a p-electron-deficient chain-folding polydiimide to afford thermally healable polymer blends. Model compounds were developed to assess the suitability of the deep green complexes formed between perylene residues and chain-folding bis-diimides for use in polymer blends. The polymer blends thus synthesised were elastomeric in nature and demonstrated healable properties as demonstrated by scanning electron microscopy. Healing was observed to occur rapidly at ca. 75 C, and excellent healing efficiencies were found by tensometric and rheometric analyses. These tuneable, stimuli-responsive, supramolecular polymer blends are compared to related healable blends featuring pyrene-terminated oligomers.

Mimicking Human and Biological Skins for Multifunctional Skin Electronics

“…Although this approach provides a reliable healing process, unfortunately it has an inherently limited healing cycle and local function depletion after the healing process . As another self‐healing mechanism, intrinsic self‐healing autonomously recovers the initial mechanical and electrical properties by dynamic covalent interactions or noncovalent interactions in a supramolecular system, such as hydrogen bonding, metal–ligand interactions, π–π interactions, and electrostatic interactions …”

The underlying mechanisms for self-healing of poly(disulfide)s

“…Intrinsic self-healing materials typically make use of reversible chemical or physical bonds which allows them to undergo multiple healing events and makes them very interesting for long-term use. Examples of the different types of chemistry used in intrinsic materials are molecular interdiffusion, 6 Diels-Alder/retro Diels-Alder reaction (DA), 7,8 photo-reversible networks, 9,10 radical fission/ recombination, 11 anionic reactions, 12 hydrogen bonding, 13,14 pH responsive systems, 15 p-p interactions, 16,17 metallosupramolecular, 18 host-guest interactions, 19 and vitrimers. 20 Another important type of chemical moiety used to obtain intrinsic self-healing materials, which has not been mentioned yet in the examples above, is the disulfide bond.…”

Intrinsic Self-Healing Polymers Based on Supramolecular Interactions: State of the Art and Future Directions

“…13 and Table 1, entries [11][12][13], where a multivalent poly(naphthalene tetracarboxylic diimide) polymer was mixed with bi-and trivalent pyrenyl-functionalized polymers [126][127][128], again displaying healing effects at elevated temperatures (200 C, some starting at~50 C) [128]. In many of these examples, the tensile modulus recovered up to 95% of the initial value [127], also indicating the contribution of multivalency effects [128], leading to a higher tensile strength of the final material [130].…”

“…Bivalent UPy-telechelic perfluoropolyethers (PFPEs) [67] recovered their storage modulus within 2 min of shearing at 130 C as a result of formation of hard crystalline UPy domains based on phase separation between the soft polymer backbone and the hydrogen bonding moieties. In contrast, PFPEs functionalized with alkylated UPy groups showed suppressed crystallization, resulting in an increased recovery time of the storage modulus of 18 min after shearing at 110 C [67] (Fig.…”