Modification of industrial softwood kraft lignin using Mannich reaction with and without phenolation pretreatment

Abstract

The amination of industrial softwood kraft lignin was conducted using the Mannich reaction to modify the lignin structure for value-added applications. To understand the reaction mechanism and to quantify the amount of amine groups that were introduced, different types of NMR analyses were performed. The lignin was also pretreated by phenolation to increase its reactivity and the amount of the amine groups that were introduced. The Mannich reaction was very selective at the C-5 position of the guaiacyl units and complete under acidic conditions with ∼11-fold amounts of reagents of dimethylamine and formaldehyde over either model lignin (4-hydroxy-3-methoxyacetophenone, HMAP) or industrial spruce kraft lignin (LignoBoost lignin, LBL). For LBL, 28 amine groups were introduced over 100 aromatic rings. By weight, the nitrogen content was 2.5%. The aminated lignin was found to possess a higher molecular mass, reaching a Mp of 4.9×103Da compared to the original 3.9×103Da, and with a considerably increased dispersibility, especially in a dilute aqueous solution of hydrochloric acid (pH=3), namely 5.2mg/ml. With a preceding phenolation treatment, which increased the amount of phenolic aromatic rings available for the Mannich reaction, an introduction of 42 amine groups over 100 aromatic rings, or a nitrogen content of 4.8%, was obtained, which caused a further increase of the molecular mass to 5.1×103Da (Mp) and of dispersibility in the aqueous solution of hydrochloric acid up to 32.0mg/ml. The aminated lignins with or without the phenolation pretreatment formed very stable colloidal suspensions in water, with large particle sizes (391 and 39nm), high zeta potentials (31.6 and 27.2mV), and large charge densities (1.6 and 1.2×10−7equiv./ml, respectively). The potential value-added applications of these modified lignins with high amine contents include use as surfactant chemicals, polycationic materials and slow-release fertilisers, among others.