In Situ Copolymerization Studies of Lignin, Acrylamide, and Diallyldimethylammonium Chloride: Mechanism, Kinetics, and Rheology.

In this work, free-radical polymerization of kraft lignin, acrylamide (AM), and diallyldimethylammonium chloride (DADMAC) was studied in detail. In situ nuclear magnetic resonance (NMR), rheological analysis, and particle size techniques were conducted to understand the physicochemical characteristics of this copolymerization system. The copolymerization of lignin-AM and lignin-DADMAC had activation energies of 65.7 and 69.3 kJ/mol, respectively, and followed the first-order kinetic model, which was monitored by in situ H NMR results. The highest conversions of AM and DADMAC were 96 and 68%, respectively, in the copolymerization of lignin, AM, and DADMAC at the molar ratio of 5.5:2.4:1, pH 2 and 85 °C. The results illustrated that the participation of AM in the reaction was essential for polymerizing DADMAC to lignin due to less steric hindrance of AM than DADMAC facilitating its bridging performance. The monomer conversion ratio and dynamic rheology of the reaction system indicated that lignin acted as an inhibitor in the copolymerization reaction. The particle size analysis of the reaction mixtures reflected the alteration in the size of particles from coarse particles (>300 μm) to fine particles (<10 and 10-50 μm) and suspension to colloidal systems when the reaction progressed. The oscillation study of the reaction media confirmed the gradual increase in the viscosity of the reaction media, illustrating the crosslinking of lignin, AM, and DADMAC.