Surface and Bulk Transformation of Thermomechanical Pulp Using Fatty Acyl Chlorides: Influence of Reaction Parameters on Surface, Morphological, and Thermal Properties

Abstract

A method is proposed for producing fatty acid esters of thermomechanical pulp (TMP) using fatty acids of intermediate chain length (C6-C12). The end objective is to use a stream of fatty acids produced via refining tall oil from Alberta's pulping mills. Depending on the degree of modification, these treated materials can serve either as reinforcement or as copolymers in composite applications. The effect of reaction conditions—reaction time, reaction temperature, fatty acyl concentration, and fatty acid chain length—on the degree of substitution of the pulp samples was studied. The reaction conditions were applied for each fatty acyl chloride and the pulp samples were characterized using X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, force tensiometry, time-of-flight secondary ion mass spectroscopy, atomic force microscopy, and thermal gravimetric analysis. The degree of substitution (DS) plateaued after two hours at a concentration of 0.25 M of hexanoyl chloride. These conditions were used for the other systems studied. The esterification of the pulp samples was heterogeneous as evident from both the AFM and SIMS images, because of the presence of lignin on the surface. Nevertheless, based on adhesion forces measured using AFM, the surface of the modified pulp samples was less polar. This was also confirmed via contact angle measurements. Also, the changes in chemical functionality were studied using FTIR and XPS with the appearance of peaks characteristic of C˭O (esters) and an increase in intensity of the alkyl shifts, respectively. Finally, it was found that esterification significantly improved the thermal properties of the pulp samples.