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Research Project
POLIURETANOS DERIVADOS DA LENHINA: FORMAÇÃO, CARACTERIZAÇÃO E APLICAÇÕES
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Lignin characterization by acetylation procedures
Publication . Cateto, Carolina; Rodrigues, Alírio; Barreiro, M.F.
The amount of the total hydroxyl content of lignin is of great importance in the formulation of a lignin based polyurethane system since it allows the quantity of the polyisocyanate counterpart within the right stoichiometry. In this work, the reliability of an acetylation procedure, regarding the determination of total hydroxyl content of a commercial kraft lignin, was studied. Lignin was acetylated using acetic anhydride reagent in solution in pyridine and the recovered acetylated samples were analysed by FTIR using KBr pellets. The experimental variables investigated were: reaction time, reaction temperature, composition of the acetylation reagent, presence of a catalyst and drying process of the acetylated samples. Within this work, the obtained results indicate that acetylation was incomplete for all the studied conditions, resulting in an unreliable total hydroxyl determination and shows the limitation of this technique.
This observation is in accordance with recent published works (see, for example, Gosselink et al., 2004) and could justify the lack of agreement among some published experimental results concerning interlaboratory analysis.
Bioactivity evaluation of four technical lignins: Alcell, Indulin-AT, Sarkanda and Curan 27-11P
Publication . Marques, A.; Cateto, Carolina; Calhelha, Ricardo C.; Barros, Lillian; Queiroz, Maria João R.P.; Belgacem, Mohamed Naceur; Rodrigues, Alírio; Ferreira, Isabel C.F.R.; Barreiro, M.F.
In what concerns bioactive properties, and due to its phenolic
character, lignin is mostly studied for their antioxidant activity.
In this work four technical lignins (Alcell, Indulin-AT, Sarkanda
and Curan 27-11P) have been evaluated for their antioxidant
activity (DPPH radical scavenging activity, reducing power and
inhibition of β-carotene bleaching) and antitumor potential
against MCF-7, NCI-H460, HCT-15, HeLa and HepG2 cell
lines. Additionally, the toxicity for non-tumour cells (PLP2) was
also evaluated. The obtained results were correlated with the
chemical and structural features of the studied lignins. Based on
the achieved results, lignins of GS type, i.e. lignins rich in
syringyl phenol units and poor in p-hydroxyphenyl ones result in
better antitumor potential.
Kinetic study of the formation of lignin-based polyurethanes in bulk
Publication . Cateto, Carolina; Barreiro, M.F.; Rodrigues, Alírio; Belgacem, Mohamed Naceur
The formation of lignin-based polyurethanes was monitored by Fourier transform infrared spectroscopy
working in attenuated total reflectance mode (FTIR-ATR) and kinetics was analyzed according to a global
second order model. The used chemical system consisted of 4,40-methylene-diphenylene diisocyanate
(MDI), polycaprolactone (PCL) of three different average-molecular weights (400, 750 and 1000) and
two lignin (L) samples (Alcell (A) and Indulin AT (IAT)), incorporated at different weight contents (10%,
15%, 20% and 25%) in the polyol mixture. The polymerization reaction was carried in bulk and without
the presence of any catalyst. Results showed that isocyanate conversion decreases with the increase of
both lignin content and PCL molecular weight. Moreover, the Indulin AT series leaded to lower isocyanate
conversions compared to Alcell counterparts. The global second order treatment showed to be dependent
of lignin type and content as well as PCL molecular weight. In fact, for the studied system this model was
found to be more adequate for low lignin contents. After the region of linearity, a negative deviation was
always observed and found to be more pronounced with increasing the lignin content.
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Fundação para a Ciência e a Tecnologia
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Funding Award Number
SFRH/BD/18415/2004