Supramolecular Polymer Network based on Electrophilic Substitution (ES) Adduct of Furan-Triazolinedione.

Polymers with furan functionality have been the subject of extensive research on developing sustainable materials applying a limited number of dynamic covalent approaches. Herein, we introduce a facile, dynamic non-covalent approach to make a furan polymer readily accessible for self-healing applications based on its electrophilic substitution (ES) with a commercially available 1,2,4-triazoline-3,5-dione (TAD) derivative, 4-phenyl-TAD (PTAD). A tailor-made furan polymer, poly(furfuryl methacrylate) (PFMA), considering it an initial illustrative example, was rapidly ES modified with PTAD to produce furfuryl-tagged triazolidine that subsequently associated via inter-molecular hydrogen (H-) bonding to produce a thermally reversible supramolecular polymer network under ambient conditions. The H-bonded network was experimentally quantified via ATR-IR analysis and theoretically rationalized via the density functional theory (DFT) study using smaller organic model compounds analogous to the macromolecular system. Thermoreversible feature of the H-bonded triazolidine-derived supramolecular polymer network enabled the solution reprocessing and self-healing of the polymer material.

Reversible Postsynthetic Modification in a Metal-Organic Framework.

Postsynthetic modification (PSM) of metal-organic frameworks (MOFs) provides access to functional materials and advanced porous solid engineering. Herein, we report the reversible PSM of a multivariate isoreticular MOF by applying dynamic furan-maleimide Diels-Alder (DA) chemistry. The key step involves incorporating a furan group into the MOF via "click" PSM, which can then undergo repeated cycles of modification and de-modification with maleimides. The structural integrity, crystallinity, and porosity of the furan-appended MOF remained intact even after three consecutive PSM/de-modification cycles using three different functionalized maleimides.

Correction: Self-healing mixed matrix membranes containing metal-organic frameworks.

[This corrects the article DOI: 10.1039/D2SC04345A.].

Self-healing mixed matrix membranes containing metal-organic frameworks.

Mixed-matrix membranes (MMMs) provide a means to formulate metal-organic frameworks (MOFs) into processable films that can help to advance their use in various applications. Conventional MMMs are inherently susceptible to craze or tear upon exposure to impact, cutting, bending, or stretching, which can limit their intended service life and usage. Herein, a simple, efficient, and scalable in situ fabrication approach was used to prepare self-healing MMMs containing Zr(iv)-based MOFs. The ability of these MMMs to self-heal at room temperature is based on the reversible hydrolysis of boronic-ester conjugates. Thiol-ene 'photo-click' polymerization yielded robust MMMs with ∼30 wt% MOF loading and mechanical strength that varied based on the size of MOF particles. The MMMs could undergo repeated self-healing with good retention of mechanical strength. In addition, the MMMs were catalytically active toward the degradation of the chemical warfare agent (CWA) simulant dimethyl-4-nitrophenyl phosphate (DMNP) with no change in activity after two damage-healing cycles.

Self-healable hydrophobic polymer material having urethane linkages via a non-isocyanate route and dynamic Diels-Alder 'click' reaction.

Conventional synthesis of polyurethane (PU) often involves the use of inherently toxic and overly moisture-sensitive isocyanates. Herein, we report the preparation of a self-healable hydrophobic polymer network having urethane linkages via a facile non-isocyanate route based on carbonylimidazole-amine reaction and dynamic Diels-Alder (DA) 'click' reaction based on furan-maleimide cycloaddition. This isocyanate-free DA 'clicked' polymer material showed excellent self-healing and hydrophobic characteristics.

A healable thermo-reversible functional polymer prepared via RAFT polymerization and ultrafast 'click' chemistry using a triazolinedione derivative.

This communication reports the preparation and characterization of a functional polymer bearing a pendant indole group via a reversible-addition fragmentation and chain transfer (RAFT) process followed by its modification via an Alder-ene 'click' reaction using a 1,2,4-triazoline-3,5-dione (TAD) derivative. The resultant functional polymer showed thermo-reversible as well as healing characteristics.