ABSTRACT
All-lignin coating formulations were prepared while combining water-soluble cationic kraft lignin (quaternized LignoBoost®, CL) and anionic lignosulphonate (LS). The electrostatic attraction between positively charged CL and negatively charged LS led to the formation of insoluble self-organized macromolecule aggregates that align to films. The structures of the formed layers were evaluated by atomic force microscopy (AFM), firstly on glass lamina using dip-coating deposition and then on handsheets and industrial uncoated paper using roll-to-roll coating in a layer-by-layer mode. Coated samples were also characterized by optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM/EDS), and contact angle measurements. It was suggested that the structure of all-lignin aggregates is the result of the interaction of amphiphilic water-soluble lignin molecules leading to their specifically ordered mutual arrangement depending on the order and the mode of their application on the surface. The all-lignin coating of cellulosic fiber imparts lower air permeability and lower free surface energy to paper, mainly due to a decrease in surface polarity, thus promoting the paper's hydrophobic properties. Moderate loading of lignin coating formulations (5-6 g m-2) did not affect the mechanical strength of the paper.
ABSTRACT
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.
ABSTRACT
The detailed chemical composition of the lipophilic extractives of cork and cork byproducts generated throughout industrial processing has been investigated by gas chromatography-mass spectrometry. Triterpenes (cerine, friedeline, and betulinic acid) were the major components detected. Betulinic acid is the main triterpene (11.7 g/kg) identified in industrial cork powder, whereas in black condensates friedeline (95.3 g/kg), betuline (13.1 g/kg), and betulinic acid (12.1 g/kg) are the main triperpenes. Significant fractions of alpha-hydroxy fatty acids (115.1 g/kg) and alpha,omega-dicarboxylic acids (21.2 g/kg) were also detected in black condensate after alkaline hydrolysis. The results demonstrate that these two industrial byproducts can be considered as promising sources of bioactive chemicals or chemical intermediates for the synthesis of polymeric materials.
