Developing sustainable polymers with low-value lignin remains a challenge. Herein, lignin-containing repairable polyimines were synthesized with tailored properties using lignin fractionation. First, softwood Kraft lignin is fractionated into a more homogeneous fraction with a lower molecular weight and a higher OH content. Next, Kraft lignin and its fraction are esterified by levulinic acid to introduce active ketone groups and subsequently condensed with oleylamine (OAm) and bis(3-aminopropyl)-terminated polydimethylsiloxane (PDMS) via a catalyst-free Schiff-base reaction to form grafted lignin-OAm copolymers and cross-linked lignin-PDMS polymer networks (MKL-P and MFL-P), respectively. Results show that lignin-OAm polyimines can be self-repaired and hot reprocessed under pressure, while lignin-PDMS polyimines can be repaired with the assistance of a healing agent, heat, and pressure. Dynamic mechanical analyses demonstrate that the stress–relaxation behaviors of the polyimines follow the Arrhenius law under thermal-stress activation, indicating the occurrence of transimination. Moreover, compared with Kraft lignin, the lignin fraction ameliorates the grafting density of ketones and enhances the cross-linking density of lignin-PDMS polyimine networks. The higher cross-linking density of MFL-P leads to superior stress–relaxation activation energy, thermal stability, hydrophobicity, and light-shielding ability but inferior repairability and translucency. This work provides insights into the polymerization of lignin-based polymer networks and the potential application of lignin-PDMS polyimines for repairable, translucent, anti-UV, and hydrophobic coatings.
