Facultad Regional San Francisco
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Item Mechanistic insight into hydroxy‑methylation of hardwood kraft lignin(2024-09-24) Peralta, Micaela; Pajer, Nicolò; Crestini, Claudia; Nicolau, Verónica V.In view of developing upcycling strategies for hardwood Kraft lignin, hydroxymethylation of Eucalyptus Kraft lignin under alkaline conditions (pH 9 and 11) at different temperatures (50 °C and 70 °C) was studied in the present effort with the double objective of optimizing the reaction conditions and understanding the functionalization mechanism of C5 in either terminal or internal guaiacyl units during hydroxy-methylation. Formaldehyde consumption was estimated via titration of the oximated free formaldehyde; the hydroxy-methylation degree under the reaction was estimated by calculating the ratio in Condensed hydroxyl/Guaiacyl (Condensed OH/G-OH) via a new difference UV-spectroscopy. The reliability of the difference UV-method results for the analyses of the hydroxy-methylated lignins was statistically analysed and compared with that of vacuum-dried and sonicated samples. Hydroxy-methylated samples were then fully characterised by NMR (31P and HSQC) and GPC. The reaction temperature of 50 °C, pH 11, and period time of one hour resulted as the optimal conditions for the hydroxy-methylation, preventing the side-reactions leading to the formation of dimethylene-glycol addition products.The 31P and 1H–13C HSQC NMR revealed the absence of undesirable formaldehyde Cannizzaro by-products and the lack of hydroxymethyl groups in the aliphatic side chain under the studied conditions. GPC analyses, comparing two methodologies, revealed increases in molar mass of the hydroxy-methylated samples upon the formaldehyde addition. The selective hydroxy-methylation at the C5 guaiacyl site demonstrates that Eucalyptus Kraft lignin is as a promising candidate for resolproductionItem Development of a bio-based high pressure laminate (HPL) by partial replacement of phenol with hardwood kraft lignin: design, optimization and scaling-up(GEP-SLAP, 2022-05) Peralta, Micaela; Nicolau, Verónica V.This work involved the design, optimization and scaling-up of the Hx process of a eucalyptus KL for resol synthesis and HPL production. Variables such as pH, temperature, and order of conditioning of reagents were studied during the laboratory optimization of the Hx to favor dissolution and increase KL reactivity. Scaling-up was performed at Centro S.A., San Francisco, Córdoba, Argentina. The hydroxymethylated KL (HL) was employed for the substitution of 30 wt% P in resol synthesis. The lignin-phenol-formaldehyde (LPF) and conventional PF resins were characterized and employed for the industrial impregnation of Kraft-type paper and subsequent curing. Tensile and flexural tests of HPL were performed. Also, boiling water resistance test was performed.Item Determinación de grupos hidroxilo fenólicos reactivos en lignina Kraft de madera dura por titulación acuosa potenciométrica(AJEA- Actas de Jornadas y Eventos Académicos de UTN, 2023-12) Peralta, Micaela; Dobler, Santiago; Lesta, Mateo Ariel; Nicolau, Verónica V.Las ligninas Kraft son polímeros naturales polifenólicos de estructura compleja cuya baja reactividad puede sortearse mediante la activación por hidroximetilación con incorporación de grupos hidroximetilo reactivos necesarios en la fabricación de poliuretanos y adhesivos fenólicos. El trabajo experimental consistió en la optimización de una técnica potenciométrica para la determinación de grupos hidroxilo fenólicos y su monitoreo durante la funcionalización de una lignina de madera dura por hidroximetilación a temperaturas de 50 y 70 °C y pH 9 y 11. La optimización de la técnica potenciométrica permitió una reducción del 38 % en el tiempo de pretratamiento total de la muestra. La lignina hidroximetilada a pH 11 y 70 °C exhibió la mayor conversión (31 %) de grupos hidroxilo fenólicos.