Application of Sulphur-Free Lignins as a Filler for Elastomers: Effect of Hexamethylenetetramine Treatment

Paola Frigerio, Luca Zoia, Marco Orlandi, Thomas Hanel, Luca Castellani


Lignins from a steam explosion process in crude and purified forms and modified sulphur-free commercial lignin (Protobind 3000®) were characterised to establish their chemical compositions. Then, the lignins were tested again after treatment with hexamethylenetetramine (HMT). The resulting products were used to make rubber composites, and their mechanical properties were compared to rubber composites made with carbon black to test the possibility of using HMT-treated lignins as a partial replacement for carbon black in the production of rubber composites. In the crude lignin, a significant amount of impurities were detected, such as ash and residual polysaccharides, and these substances interfered in filler-elastomer interactions. The purified lignin maintained a high content of strongly polarised hydroxyl groups that interfered with the interaction of the filler and elastomer, resulting in low performance. Improvements in the mechanical properties were observed using Protobind 3000® lignin or purified lignin with HMT added during mixing with the rubber. Finally, the mixing of HMT-treated lignin with elastomers resulted in composites with higher reinforcement abilities compared to previously described rubber composites. However, in all samples, a poor and unsatisfactory dispersion of lignin in the polymeric matrix was observed. This is likely due to the incompatibility of lignin with the hydrophobic rubber, resulting in lower performances compared to the carbon black.


Lignin; Hexamethylenetetramine; Rubber composites; Mechanical properties; Dispersion; Particle size

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