Lignin-phenol-formaldehyde (LPF) resoles were prepared using different types of lignin at various levels of phenol replacement by lignin (0 to 40 wt.%). Adhesive properties including thermal behavior as determined by differential scanning calorimetry (DSC), time-dependent development of bond strength during hot pressing as determined by automated bonding evaluation system (ABES), tensile shear strength of solid beech wood lapjoints, and free formaldehyde content of the adhesives were investigated. Preparation of phenol-formaldehyde (PF) resole was accomplished using molar ratios of formaldehyde/phenol and NaOH/phenol of 2.5 and 0.3, respectively. Four different types of technical lignins were studied: Sarkanda grass soda lignin, wheat straw soda lignin, pine kraft lignin, and beech organosolv lignin. The synthesis of the resoles was optimized for 20 and 40 wt.% phenol replacement by lignin. Increasing substitution of phenol resulted in faster gain of LPF viscosity for all studied lignins. The best curing performances of the LPF resoles were observed for pine kraft lignin at both 20 and 40% phenol replacement. The amount of formaldehyde not consumed during cooking increased with increasing level of phenol replacement. However, no differences in free formaldehyde content were observed between the different lignin samples at comparable levels of phenol replacement.

Four commercial spruce lignosulfonates representing the most common acidic, neutral, and alkaline sulfite pulping processes and varying significantly in molecular weight characteristics were tested as partial (40 wt %) phenol substitute materials for the manufacture of lignosulfonate‐phenol‐formaldehyde (LPF) resole resins. Similar as recently reported for technical lignins from nonsulfite pulping processes (kraft, soda, organosolv), all lignosulfonates of this study effectuated a faster viscosity gain during resole cooking compared to the lignin‐free reference resin (1000 mPa s after 120 min vs. 250 min to reach 1000 mPa s). Sodium lignosulfonate featuring the lowest weight average molecular weight (Mw 5780 g mol−1) and dispersity (Ð 6.1) turned out to be superior to the other lignosulfonates with regard to curing rate (B‐time; 3:37 min vs. 6:41–9:08 min) and tensile shear strength development under hot pressing (120 °C; TS,max = 5.64 N mm−2 after 8 min) for beech veneer strips glued together with the respective LPF resins. Calcium and magnesium lignosulfonates are less suited with regard to phenol replacement due to the poor performance of the respective LPF adhesives in terms of tensile shear strength (TS,max = 3.29–3.49 N mm−2 after 12 min) most likely caused by considerable amounts of side products formed in the course of formose‐type reactions. Phenolation of the two promising lignosulfonates, that is, sodium and ammonium lignosulfonate, did neither considerably increase the rate of PF network formation during resin cooking and curing nor improve tensile strength development during hot pressing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45893.

Ammoxidation of pine kraft lignin in aqueous 5 wt % ammonia affords a novel type of phenol substitute that significantly accelerates resole synthesis and curing as demonstrated for 40 wt % phenol replacement. Compared to non-ammoxidized lignin, which already shortens significantly the cooking time required to reach a resole viscosity of 1000 Pa·s (250 vs. 150 s) and reduces the typical curing B-time by about 25% at 100 • C, the use of ammoxidized lignin has an even more pronounced impact in this respect. Activation of lignin by Fenton-type oxidation prior to ammoxidation further boosts both synthesis and curing of the resole. This is presumably due to the intermediary formation of polyvalent cross-linkers like N,N,N-tris (methylol) trimethylene triamine triggered by saponification of a larger fraction of nitrogenous moieties present in such a treated lignin (ammonium salts, amide-type nitrogen, urea) and reaction of the released ammonia with formaldehyde. Except for the fact that phenol replacement by ammoxidized lignin results in a somewhat less brittle cured adhesive polymer and higher elastic modulus, the aforementioned acceleration in curing could no longer be observed in the presence of wood, where a significantly delayed wood-adhesive bond formation was observed for the lignin-containing adhesives as evident from the automated bonding evaluation system.

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography (M w 2180 Da), and quantitative 13C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes.