Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues

Abstract

The functionality inherent in lignin-derivable bisguaiacols/bissyringols can improve the processability and performance of the resulting polymers. Herein, non-isocyanate polyurethanes (NIPUs) were synthesized from bisguaiacols/bissyringols with varying degrees of methoxy substitution and differing bridging groups. Notably, the presence of increasing numbers of methoxy groups (0, 2, and 4) in bisphenol F (BPF)-, bisguaiacol F (BGF)-, and bissyringol F (BSF)-NIPUs led to higher percentages of hydrogen-bonded –OH/–NH groups (i.e., ∼65%, ∼85%, ∼95%, respectively). Increased hydrogen bonding between chains improved the elongation-at-break (ε_break) and toughness of lignin-derivable NIPUs over their petroleum counterparts without a reduction in Young's moduli and tensile strengths. For example, BSF-NIPU exhibited the highest ε_break ∼210% and toughness ∼62 MJ m⁻³, followed by BGF-NIPU (ε_break ∼185% and toughness ∼58 MJ m⁻³), and then BPF-NIPU (ε_break ∼140% and toughness ∼42 MJ m⁻³). Similar trends were found in the dimethyl-substituted analogues, particularly for the bisphenol A-NIPU and bisguaiacol A-NIPU. Importantly, the melt rheology of the lignin-derivable NIPUs was comparable to that of the petroleum-derived analogues, with a slightly lower viscosity (i.e., improved melt flow) for the bio-derivable NIPUs. These findings suggested that the added functionalities (methoxy groups) derived from lignin precursors improved thermomechanical stability while also offering increased processability. Altogether, the structure–property-processing relationships described in this work can help facilitate the development of sustainable, performance-advantaged polymers.