Bio-based vitrimers represent a promising class of thermosetting polymer materials, pairing the recyclability of dynamic covalent networks with the renewability of non-fossil fuel feedstocks. Vanillin, a low-cost lignin derivative, enables facile construction of polyimine networks marked by rapid exchange and sensitivity to acid-catalyzed hydrolysis. Furthermore, the aromatic structure makes it a promising candidate for the design of highly aromatic networks capable of high-performance thermal and dimensional stability. Such properties are paramount in polymeric thermal protection systems. Here, we report on the fabrication of polyimine networks with particularly high aromatic content from a novel trifunctional vanillin monomer prepared from the nucleophilic aromatic substitution of perfluoropyridine (PFP) on a multi-gram scale (>20 g) in high yield (86%). The trifunctional aromatic scaffold was then crosslinked with various diamines to demonstrate tunable viscoelastic behavior and thermal properties, with glass transition temperatures (Tg) ranging from 9 to 147 °C, degradation temperatures (5% mass loss) up to approximately 370 °C, and excellent char yields up to 68% at 650 °C under nitrogen. Moreover, the vitrimers displayed mechanical reprocessability over five destruction/healing cycles and rapid chemical recyclability following acidic hydrolysis at mild temperatures. Our findings indicate that vitrimers possessing tunable properties and high-performance thermomechanical behavior can be easily constructed from vanillin and electrophilic aromatic scaffolds for applications in heat-shielding materials and ablative coatings.
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