Hydrodynamic alignment and self-assembly of cationic lignin polymers made of architecturally altered monomers

Cationic kraft lignin (CKL) polymers with different degrees of grafting (35.2-125.5 mol%) were synthesized via polymerizing kraft lignin (KL) and [2-(acryloyloxy)ethyl]trimethylammonium chloride (ATAC) or [2 (methacryloyloxy)ethyl]trimethylammonium methyl sulfate (METAM) to investigate the impact of the chain extension of the polymers on the physicochemical behavior of CKL in an aqueous solution. It was observed that, at the same grafting ratio, the structural difference of CKLs influenced their hydrophilicity, in which the contact angle of KL-METAM and KL-ATAC solution (1 g/L) reached 9.4° and 11.8° on a glass slide, respectively, at the maximum degree of grafting of ~125 mol%. KL-METAM had a more three-dimensional and flexible structure than KL-ATAC in solution, which promoted its self-assembly (with the aggregate diameter of 235-532 nm) and sedimentation (with the TSI value of 16.8). The rheological studies confirmed the more elasticity of KL-METAM than KL-ATAC with the elastic modulus of 9.3 and 8 Pa at the highest frequency. Quartz crystal microbalance (QCM) adsorption studies illustrated that KL-METAM adsorbed more greatly and generated a bulkier and more viscoelastic adlayer than KL-ATAC did on a rigid surface, below saturation (ΔD/Δf slope of 0.13-0.45) and at equilibrium (ΔD/Δf slope of 0.02-0.17). For the deposited adlayer, the alterations in the slope of dissipation/frequency (ΔD/Δf) between the early and late stages of adsorption were claimed to be related to the conformational changes of CKLs upon adsorption. The findings of this study showed that the architecture of cationic monomers could affect the structure of CKLs so significantly that the lignin polymers would have different chain conformations and flexibility in solution, varied rheological properties, and adsorption performance on a solid surface. The significance of the monomer architecture on the properties and performance of CKLs was more observable at a higher grafting ratio.