Application of a Universal Calibration Method for True Molar Mass Determination of Fluoro-Derivatized Technical Lignins by Size-Exclusion Chromatography

The determination of the true molar mass distribution (MMD) of lignin is highly important to understand the physicochemical characteristics for lignin-based value-added applications. It is imperative to develop a universal method to quantify accurate MMD of lignin using size exclusion chromatography (SEC), as the conventional method with polymer standards provides irregular MMD results. This work aims to evaluate the MMD of five lignin samples (Protobind 1000, Organosolv, Indulin, Pine Kraft and Eucalyptus Kraft) in THF. Different derivatization methods (acetylation, fluorobenzylation and fluorobenzoylation) were performed. FTIR and 19F NMR analyses were used to follow derivatization. The MMDs of derivatized and underivatized lignins were determined by the conventional method and compared with the universal calibration method developed using intrinsic viscosity. The 19F NMR spectra provided the information to quantify the degree of substitution of lignin hydroxyl groups, to calculate the true molar mass of the derivatives of lignin monomers. The obtained MMDs values for all the derivatized lignin by universal calibration were found to be three to five times higher than that of the conventional calibration. The polydispersity values obtained with the acetylation method were higher than the fluoro-derivatives. The results demonstrated that fluoro-derivatization is an appropriate method to apply to higher molar mass technical lignins and lacks solubility and aggregation issues

Study of new chemical derivatization techniques for lignin analysis by size exclusion chromatography

La lignine, deuxième biopolymère le plus abondant sur Terre, possède une structure aromatique tridimensionnelle hautement ramifiée, porteuse de différents groupements fonctionnels, principalement alcooliques et phénoliques. Le travail de recherche a porté sur les méthodes de dérivation chimique de la lignine permettant de quantifier les hydroxyles et de déterminer les distributions de masses molaires des lignines par chromatographie d’exclusion stérique et multi-détection. Cinq lignines techniques ont été étudiées : Protobind 1000, Organosolv (CIMV), lignine Kraft de pin, lignine Kraft d’Eucalyptus et lignine Indulin. L’acétylation, méthode classique de dérivation des hydroxyles, a été comparée aux nouvelles méthodes de fluoro-dérivation développées durant l’étude (fluorobenzylation et fluorobenzoylation). Les fonctions hydroxyle ont été quantifiées par titrages conductimétriques et potentiométriques, aminolyse-GC, spectrométries IR et UV- différentielle, et spectrométrie RMN (1H, 13C, 19F et 31P). La distribution des masses molaires des lignines dérivées a été déterminée en utilisant différentes colonnes et solvants (DMAc et THF). La méthode d’étalonnage standard, utilisant différents polymères standards de calibration, et la méthode dite “d’étalonnage universel”, utilisant la détection viscosimétrique couplée à la réfractométrie, ont été comparées. La fluoro-dérivation augmente la solubilité de la lignine dans le THF et améliore les résultats chromatographiques. L'étalonnage universel conduit à environ trois fois les valeurs de masses molaires calculées par étalonnage standard.Lignin is the second most abundant biopolymer on earth and it consists of highly-branched, three dimensional aromatic structures with variety of functional groups, mainly phenolic and alcoholic functions. This research work was focused on derivatization methods to quantify hydroxyl groups in lignins and to determine lignin molar mass distribution by size-exclusion chromatography coupled to multi-detectors. Five different technical lignins were studied: Protobind 1000, Organosolv (CIMV), Pine Kraft, Eucalyptus Kraft and Indulin. Lignin samples were washed and derivatized by classical acetylation, which was compared to fluoro-derivatization using the new methods developed in this work, such as fluorobenzylation and fluorobenzoylation. Hydroxyl groups present in the lignin samples were quantified by potentiometric and conductometric titrations, GC-aminolysis, IR and differential UV spectroscopies and NMR spectroscopy (1H, 13C, 19F and 31P). Molar mass distributions of derivatized lignins were calculated using different columns and solvents (DMAc and THF). Conventional calibration, using different standard polymers as calibrants, was compared to the so-called “universal calibration method”, which uses viscometric and refractometric detectors. Fluoro-derivatization enhanced lignin solubility in THF and improved chromatographic results. Universal calibration led to about three times higher molar mass values than by conventional calibration

Etude de nouvelles techniques de dérivation chimique de la lignine en vue de l'analyse par chromatographie d'exclusion stérique

Lignin is the second most abundant biopolymer on earth and it consists of highly-branched, three dimensional aromatic structures with variety of functional groups, mainly phenolic and alcoholic functions. This research work was focused on derivatization methods to quantify hydroxyl groups in lignins and to determine lignin molar mass distribution by size-exclusion chromatography coupled to multi-detectors. Five different technical lignins were studied: Protobind 1000, Organosolv (CIMV), Pine Kraft, Eucalyptus Kraft and Indulin. Lignin samples were washed and derivatized by classical acetylation, which was compared to fluoro-derivatization using the new methods developed in this work, such as fluorobenzylation and fluorobenzoylation. Hydroxyl groups present in the lignin samples were quantified by potentiometric and conductometric titrations, GC-aminolysis, IR and differential UV spectroscopies and NMR spectroscopy (1H, 13C, 19F and 31P). Molar mass distributions of derivatized lignins were calculated using different columns and solvents (DMAc and THF). Conventional calibration, using different standard polymers as calibrants, was compared to the so-called “universal calibration method”, which uses viscometric and refractometric detectors. Fluoro-derivatization enhanced lignin solubility in THF and improved chromatographic results. Universal calibration led to about three times higher molar mass values than by conventional calibration.La lignine, deuxième biopolymère le plus abondant sur Terre, possède une structure aromatique tridimensionnelle hautement ramifiée, porteuse de différents groupements fonctionnels, principalement alcooliques et phénoliques. Le travail de recherche a porté sur les méthodes de dérivation chimique de la lignine permettant de quantifier les hydroxyles et de déterminer les distributions de masses molaires des lignines par chromatographie d’exclusion stérique et multi-détection. Cinq lignines techniques ont été étudiées : Protobind 1000, Organosolv (CIMV), lignine Kraft de pin, lignine Kraft d’Eucalyptus et lignine Indulin. L’acétylation, méthode classique de dérivation des hydroxyles, a été comparée aux nouvelles méthodes de fluoro-dérivation développées durant l’étude (fluorobenzylation et fluorobenzoylation). Les fonctions hydroxyle ont été quantifiées par titrages conductimétriques et potentiométriques, aminolyse-GC, spectrométries IR et UV- différentielle, et spectrométrie RMN (1H, 13C, 19F et 31P). La distribution des masses molaires des lignines dérivées a été déterminée en utilisant différentes colonnes et solvants (DMAc et THF). La méthode d’étalonnage standard, utilisant différents polymères standards de calibration, et la méthode dite “d’étalonnage universel”, utilisant la détection viscosimétrique couplée à la réfractométrie, ont été comparées. La fluoro-dérivation augmente la solubilité de la lignine dans le THF et améliore les résultats chromatographiques. L'étalonnage universel conduit à environ trois fois les valeurs de masses molaires calculées par étalonnage standard

Lignin model compounds fluorobenzylation

International audienc

Study of the Reactivity of Lignin Model Compounds to Fluorobenzylation Using 13C and 19F NMR: Application to Lignin Phenolic Hydroxyl Group Quantification by 19F NMR

International audienceLignin is an aromatic biopolymer derived from lignocellulosic biomass. Providing a comprehensive structural analysis of lignin is the primary motivation for the quantification of various functional groups, with a view to valorizing lignin in a wide range of applications. This study investigated the lignin fluorobenzylation reaction and performed a subsequent 19F-NMR analysis to quantify hydroxyl groups, based on a work developed two decades ago by Barrelle et al. The objectives were to check the assignments proposed in this previous study and to examine the reactivity of various types of lignin hydroxyls with the derivatization agent. Selected lignin model compounds containing phenolic and aliphatic hydroxyls were subjected to the fluorobenzylation reaction, and the obtained reaction medium was analyzed by 13C and 19F NMR spectroscopy. The model compound results showed that phenolic hydroxyls were totally derivatized, whereas aliphatic hydroxyls underwent minimal conversion. They also confirmed that 19F NMR chemical shifts from −115 ppm to −117.3 ppm corresponded to phenolic groups. Then, a 19F NMR analysis was successfully applied to Organosolv commercial lignin after fluorobenzylation in order to quantify its phenolic group content; the values were found to be in the range of the reported values using other analytical techniques after lignin acetylation

The Potential Value of Debarking Water as a Source of Polyphenolic Compounds for the Specialty Chemicals Sector

Forest-based industries produce huge quantities of bark during their primary processing activities. In Nordic pulp and paper industries, where a wet debarking process is used for bark removal, toxic debarking water and bark press water are produced as a by-product. However, polyphenols represent an important fraction of the debarking water and bark press water. These polyphenolic compounds are of commercial interest in chemical specialty sectors since polyphenols have been proven to have diverse health benefits, and after collecting them from waste sources, they can act as alternatives to oil-based chemicals. Determining the economic potential of polyphenolic compounds, identifying their molecular structure, and determining the antioxidant capacity of these compounds present in debarking water and bark can support the identification of their potential applications. The results show that water extractions from bark have a lower efficiency than (partial) alcoholic extractions. Nevertheless, a considerable amount of low-molecular polyphenolic compounds, which are of interest for high-end applications, was found in all extracts. Bark press water has a highly versatile range of polyphenolic compounds and showed some antioxidant activity, making it a great source for the collection of polyphenolic compounds, in contrast to debarking water, which had a much lower polyphenolic content and low antioxidant activity