aCork is one of the most important forest products in Portugal. The cork processing industry is highly resource-efficient, and the only residue is cork powder, which is too small for agglomerate production. This work studied the usage of cork powder for the production of added-value products via polyol liquefaction. Liquefactions were performed in a reactor using a mixture of polyethylene glycol (PEG 400) and glycerol as solvents, which were catalyzed by the addition of sulphuric acid. Several cork-tosolvent ratios, reaction temperatures, and reaction times were tested. Polyurethane foams were prepared by combining polyol mixtures with a catalyst, surfactant, blowing agent, and polymeric isocyanate. Mechanical tests of the produced foams were conducted, and compressive modulus of elasticity and compressive stress at 10% deformation were determined. The results show that the best conditions for obtaining high liquefaction yields are as follows: 160 °C for 1 h; glycerol-to-PEG 400 ratio of 1:9; corkto-solvent ratio of 1:6; and 3% H2SO4 catalyst addition. The Fourier Transform Infrared (FTIR) spectra indicated that the lignocellulosic fractions of the cork were more selectively dissolved during acidified polyol liquefaction than the suberin. With liquefied cork powder using these optimized conditions, it is possible to produce polyurethane foams with desired properties.
The chemical structure of lignin from grape stalks, an abundant waste of winemaking, has been studied. The dioxane lignin was isolated from extractive- and protein-free grape stalks (Vitis vinifera L.) by modified acidolytic procedure and submitted to a structural analysis by wet chemistry (nitrobenzene and permanganate oxidation (PO)) and spectroscopic techniques. The results obtained suggest that grape stalk lignin is an HGS type with molar proportions of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units of 3:71:26. Structural analysis by (1)H and (13)C NMR spectroscopy and PO indicates the predominance of β-O-4' structures (39% mol) in grape stalk lignin together with moderate amounts of β-5', β-β, β-1', 5-5', and 4-O-5' structures. NMR studies also revealed that grape lignin should be structurally associated with tannins. The condensation degree of grape stalks lignin is higher than that of conventional wood lignins and lignins from other agricultural residues.
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