Fully Bio-Based Cellulose Vitrimers with Dynamic Enamine Bonds: Toward Recyclable and Micropatternable Green Materials

Abstract

The development of high-performance and recyclable materials from renewable resources remains a significant challenge in polymer science. Vitrimers, featuring dynamic covalent crosslinked networks, offers an attractive platform to harmonize mechanical robustness with reprocessability. Herein, we report a fully bio-based vitrimer fabricated through a catalyst-free dynamic crosslinking of cellulose acetoacetate (CAA) with a plant oil derived diamine (Priamine 1075). The resulting cellulose-Priamine (CP) vitrimer network incorporates enamine bonds that enable catalyst-free topology rearrangement under thermal activation. Hot-pressed CP films exhibit a balanced combination of tensile strength (30 MPa) and ductility (21% elongation at break), along with rapid stress relaxation (characteristic relaxation time of 3 min at 160 °C). Notably, the material retains >90% of its mechanical properties after multiple hot-pressing cycles, and demonstrates controlled degradability under biologically relevant conditions (8 week, >90%). Moreover, the acid-responsive character of the enamine bonds unlocks a powerful, sustainable, and low-energy route to micropatterning, enabling the precise, on-demand creation of intricate microscale features through simple acid etching. This work not only presents a novel strategy for designing robust, recyclable cellulose-based materials, but also provides valuable insights into the molecular engineering of bioderived dynamic networks for sustainable advanced applications.