Lignin is a widely abundant renewable source of phenolic compounds. Despite the growing interest on using it as a substitute for its petroleum-based counterparts, only 1 to 2% of the global lignin production is used for obtaining value-added products. Lignosulphonates (LS), derived from the sulphite pulping process, account for 90% of the total market of commercial lignin. The most successful industrial attempts to use lignin for wood adhesives are based on using this polymer as a partial substitute in phenol-formaldehyde or urea-formaldehyde resins. Alternatively, formaldehyde-free adhesives with lignin and lignosulphonates have also been developed with promising results. However, the low number of reactive sites available in lignin’s aromatic ring and high polydispersity have hindered its application in resin synthesis. Currently, finding suitable crosslinkers for LS and decreasing the long pressing time associated with lignin adhesives remains a challenge. Thus, several methods have been proposed to improve the reactivity of lignin molecules. In this paper, techniques to extract, characterize, as well as improve the reactivity of LS are addressed. The most recent advances in the application of LS in wood adhesives, with and without combination with formaldehyde, are also reviewed.

Out of the 50 to 70 million tons of lignin that are produced annually, only 1 to 2% are used for value-added products. Currently, 90% of the total market of this compound corresponds to lignosulphonates (LS). The most successful industrial attempts to use lignin for wood adhesives rely on using it as a partial substitute in phenol–formaldehyde or urea–formaldehyde resins. However, lignin’s aromatic ring presents a low number of reactive sites. Several methods have been proposed to improve its reactivity, such as prior methylolation with formaldehyde. Off-line methods are commonly applied to monitor this reaction’s progress, but this introduces a significant delay in the analysis. This study proposes a new method for in-line monitoring of the methylolation reaction using visible spectroscopy. In order to monitor the reaction progress, principal component analysis was applied to the spectra, and the obtained scores were analyzed. When these results were plotted against those obtained by the off-line methods, a satisfactory regression was obtained at 50 °C (R² = 0.97) and 60 °C (R² = 0.98) for two different LS samples. Therefore, it was concluded that visible spectroscopy is a promising technique for studying lignin methylolation.

Currently, the industrial success of bio-based adhesives remains limited, despite the growing interest in these compounds. One example is the use of lignosulfonates (LS), a byproduct from the pulp and paper industry, which requires long pressing times to ensure proper performance for wood-based panel production. This study successfully manufactured particleboards using a low press factor of 7.5 s/mm, commonly used for conventional urea-formaldehyde resins on a lab scale. To the best of our knowledge, lignin-based particleboards have never been reported using such low press factors. Thus, 3-layer boards were manufactured in which the core layer was bonded with polymeric isocyanate (pMDI), and the surface layers were bonded with LS. Propylene carbonate (PC) was used as a solvent for pMDI to improve adhesive distribution. The optimum amounts of adhesive were determined using response surface methodology: 1.3% pMDI with 2.2% PC in the core layer and 15% LS in the surface layers. These boards obeyed the requirements of standard EN 312 for general-purpose boards for use in dry conditions (type P1). Their formaldehyde content, determined through the perforator method, was equal to that of the wood mix at the maximum value set by IKEA for class E0.5.

Phenol–formaldehyde (PF) resins remain the preferred adhesive for exterior plywood, as they confer these boards their extreme weather resistance. However, their high price and toxicity has made phenol alternatives, such as technical lignins, increasingly more attractive. While many works report the use of kraft lignin, the most commercially available form are lignosulphonates (LS). However, these lack industrial success and are associated with low moisture resistance. In the current study, lignosulphonate–phenol–formaldehyde (LPF) resoles were synthesized considering a phenol replacement of 30% (w/w). Two LS samples of softwood (SLS) and hardwood (HLS) origin were compared. These samples were previously methylolated to increase their reactivity. The effectiveness of the treatment was confirmed through the Automated Bonding Evaluation System. Plywood was manufactured and tested according to EN 314 class 3 for exterior conditions, which is seldom found in the literature. Although a 35% increase in shear strength is still necessary to comply with the standard, methylolated SLS was the most promising substitute, as it resulted in the highest board performance. Notably, when this sample was used without previous methylolation, the plywood boards suffered delamination during immersion in boiling water prior to shear testing. These results reinforce the need for the methylolation of LS to increase the weather resistance of plywood.