High-value utilization of hydroxymethylated lignin in polyurethane adhesives

Lignin is a good candidate for the polymerization and chemical modification to prepare sustainable chemicals and materials, but a relatively low hydroxyl content becomes an obstacle for the preparation of lignin-based polyurethane (PU) adhesives. In order to improve its reactivity, the acetic acid lignin (AAL) was hydroxymethylated before copolymerized with isocyanate during the preparation of PU adhesives. The hydroxymethylation was carried out in an alkaline formaldehyde solution and it was found that 85 °C is the optimal temperature. On that condition, the free formaldehyde content of the corresponding product HL-6 was as low as 0.32%, while the hydroxymethyl was increased by 189.11% compared with original AAL and reached 2.92 mmol/g. In the polymerization of PU adhesives, the hydroxymethylated lignin with a higher aliphatic hydroxyl content formed a more compact three-dimensional urethane cross-linking network with isocyanate. The mechanical properties and thermal stability of the lignin-based PU adhesive were improved by 15–30 wt% in HL-6, and particularly the tensile strength was increased by 21–41 MPa, which indicated that the hydroxymethylation is an efficient way to enrich the hydroxyl in lignin, and the modified lignin is adequate to partially replace petroleum-based polyols for the preparation of PU adhesives with excellent properties.