Wood has been investigated for bioplastic production because of its abundance and biorenewability to reduce dependence on petro-based plastics. A series of experiments have been carried out to graft myristic acid, chosen as the fatty acid model, onto spruce sawdust using trifluoroacetic anhydride (TFAA) as the impelling agent without any solvent. The reaction was performed rapidly, leading to high ester content. Most of the hydroxyl groups in wood structure reacted with myristic acid, as demonstrated by FTIR and CPMAS 13C NMR. XRD measurements indicated a decrease in wood crystallinity. Myristic acid-esterified wood showed higher thermal stability by TGA and DSC and delivered several softening temperatures, as observed by TMA. Thermoplastic and translucent films were obtained after pressing at a high temperature. Scanning electron micrographs revealed that pressed esterified wood at the high temperature showed complete disappearance of fibrous structure to a smooth and homogenous surface, indicating that thermal fluidity was achieved during pressing. Esterified sawdust film also showed surface hydrophobicity by contact angle measurements.
Fatty acids (FA) and their derivatives with long alkyl chain structures are good candidates for wood esterification to confer thermoplastic properties to wood. Nevertheless, they do not react easily with hydroxyl groups of wood. In this study, we investigated the reactivity of wood with various fatty acids of different chain lengths using trifluoroacetic anhydride (TFAA) as the impelling agent in various reaction conditions. Generally, the esterification of fatty acids without solvents resulted in higher Weight Percentage Gain (WPG) and ester content than the reaction in the presence of CH2Cl2. The esterification reaction could be performed effectively at room temperature, though an increased reaction temperature provoked degradation of the esterified wood. WPG of 67% was obtained for the C3 and 253% for the C16 alkyl chain analogs, respectively. Nevertheless, the ester content was fairly uniform, with values between 10.60 and 11.81 mmol ester/gram of wood for all chain lengths. A higher quantity of reagent led to higher ester content, which tended to stabilize after a ratio of 1:4 wood and TFAA/FA. The esterification reaction was performed rapidly, with an ester content between 7.65 and 9.94 mmol ester/gram of wood being achieved only after 15 min of reaction. Fourier transform infrared spectroscopy (FTIR) analysis was performed to confirm the drastic chemical changes of wood before and after esterification. Morphological observation by scanning electron microscope (SEM), softening measurement by thermomechanical analysis (TMA), and contact angle measurements demonstrated the possibility of esterified spruce wood being applied as a new bioplastic.
8 August 2023 in Southern Forests: a Journal of Forest Science
To address the environmental impact of petroleum-derived plastics, lignocellulose esters provide a promising renewable alternative. However, research has primarily focused on linear cellulose esters, leaving raw biomass aromatic derivatives largely overlooked. Herein, we report a one-pot, room-temperature synthesis of cinnamate and benzoate esters from microcrystalline cellulose (MCC) and raw pine sawdust. A breakthrough finding reveals that pine esters consistently outperform pure MCC, achieving tensile strengths of 5–8 MPa (vs. 1–3 MPa for MCC) possibly due to a lignin-driven synergistic effect facilitating π–π stacking. The resulting films are hydrophobic (contact angles 80–100°) and fully thermoplastic. Cinnamates emerge as a technically superior and “greener” alternative to benzoates, paving the way for the direct upcycling of wood waste into sustainable packaging materials within a circular economy.
11 February 2024 in International Wood Products Journal
Density, as the most critical information for wood materials could be predicted by near-infrared (NIR) spectroscopy. Increment cores and thin wood samples of teakwood ( Tectona grandis) served as research materials for this new approach to sampling for NIR spectroscopy, explained in detail. Density data were combined with their NIR spectra data for analysis using cross-validation partial least squares regression as chemometrics to produce a density prediction model. A new approach of increment cores from teakwood stands for NIR spectroscopy measurements for density predictions resulting in a 0.34 coefficient of determination for cross-validation (R2CV) and 0.40 of R2CV for thin wood samples as the best result from the first derivative with 25 smoothing points of NIR spectra. The improvement from the previous research for density prediction accuracy resulted in an R2CV value of 0.55. The smaller diameter of the increment core sample than the NIR light beam's diameter and illuminated mixed surface (transversal and radial) are supposed to give weaker prediction accuracy by this new approach.