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

• Published in: Chemistry : a European journal Vol. 30; no. 17; pp. e202303367 - n/a
• Main Authors: Pal, Tuhin Subhra, Mondal, Prantik, Kundu, Niloy, Chakraborty, Swadhin, Ganguly, Debabrata, Singha, Nikhil K.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 20.03.2024
• Subjects: 1,2,4-triazoline-3,5-dione (TAD); Chemical bonds; Density functional theory; Dynamic supramolecular chemistry; Electrophilic substitution (ES); Furan; Healing; Infrared analysis; Macromolecules; Polymers; Reprocessing; Substitutes; Supramolecular polymers; Sustainable materials; Triazolidine; Triazolidines; Triazolidine; Electrophilic substitution (ES); Furan; 1,2,4-triazoline-3,5-dione (TAD); Dynamic supramolecular chemistry
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202303367

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. A tailor‐made homopolymer, poly(furfuryl methacrylate) (PFMA) was synthesized and engineered to a self‐healable supramolecular thermoset via electrophilic substitution (ES) with a commercially available 1,2,4‐triazoline‐3,5‐dione (TAD) derivative, 4‐phenyl‐TAD (PTAD).