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Results of a comprehensive study on the chemical structure of lignin from plantation Eucalyptus globulus Labill are presented. Lignin has been isolated by a modified mild acidolysis method and thoroughly characterized by functional group analysis, by a series of degradation techniques (nitrobenzene oxidation, permanganate oxidation, thioacidolysis, and Py-GC-MS), and (1)H and (13)C NMR spectroscopy. Plantation Eucalyptus globulus lignin was found to be of the S/G type with an extremely high proportion of syringyl (S) units (82-86%) and a minor proportion of p-hydrophenyl propane (H) units (roughly 2-3 mol %). Unknown C-6 substituted and 4-O-5' type syringyl substructures represent about 65% of lignin "condensed" structures. Eucalypt lignin showed high abundance of beta-O-4 (0.56/C(6)) structures and units linked by alpha-O-4 bonds (0.23/C(6)). The proportion of phenylcoumaran structures was relatively low (0.03/C(6)). Different kinds of beta-beta substructures (pino-/syringaresinol and isotaxiresinol types) in a total amount of 0.13/C(6) were detected. ESI-MS analysis revealed a wide molecular weight distribution of lignin with the center of gravity of mass distribution around 2500 u.

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ABSTRACT:The controlled heterogeneous partial modification of cellulose fibers with fatty acids, partially preserving the fiber structure, was investigated. The effect of reaction conditions, such as reaction time, fatty acid chain length, and solvent types (swelling and non swelling), on the extent of esterification and fiber properties was evaluated by elemental analysis, IR-ATR, X-ray diffraction, 13 C CPMAS NMR, contact angle measurement, thermogravimetry, and scanning electron microscopy. The degree of substitution (DS) increased with reaction time and with the swelling effect of the reaction medium and decreased with the fatty acids chain length. Higher the DS, higher is the decrystallization of cellulose as a result of the heterogeneous esterification reaction. The esterification with fatty acids enhanced the hydrophobic character of the fibers, but decreased their thermal stability. These properties are not strongly affected by the DS in the range investigated, viz. up to 1.4.

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Industrial hardwoods such as Eucalyptus species, Betula pendula, and Acacia mangium required different chemical charges during kraft pulping and presented distinct profiles of polysaccharides removal. The corresponding kraft pulps showed different chlorine dioxide consumption during bleaching. Woods and corresponding kraft pulps were characterized by chemical methods, 1 H and 13 C NMR spectroscopy, X-ray diffraction analysis, and gel permeation chromatography. The ease of lignin degradation and dissolution was essentially determined by differences in the proportion of syringyl and guaiacyl units and in the degree of condensation. The bleaching response was shown to be related also to the content of β-O-4 structures in the residual lignin. The relative stability of xylans during the pulping was suggested to be associated with differences in structure and molecular weight. The higher retention of Eucalyptus xylans was attributed essentially to their peculiar structure, including O-2-substituted uronic acid groups linked to other cell wall polysaccharides.