Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
-
Alexandr Arshanitsa
,
Laima Vevere
,
Oskars Bikovens
Abstract
The new organosolv process of wheat straw fractionation elaborated by Compagnie Industrielle de la matiere Vegetale (France) corresponds to the biorefinery approach, which allows separating cellulose, hemicelluloses, and lignin. The straw lignin (Biolignin™) is an attractive product, for which new applications are sought. In the present work, straw lignin (L) was converted into liquid lignopolyols via a batch reaction with propylene oxide (PO). The effects of the lignin content (L%) in the initial reaction mixture (L/(L+PO) on the oxypropylation process and the properties of whole lignopolyols and L/PO copolymers were studied. Almost complete disappearance of L-OHphen and L-COOH groups in copolymers was accompanied by an increase in the L-OHaliph groups’ content therein. The polydispersity (Mw/Mn) of all copolymers obtained decreased essentially compared to the reference. The extent of PO grafting onto OH groups increased with decreasing lignin content in the initial reaction mixture. At a lignin content of 15–30% in the initial reaction mixture, the lignopolyols fulfil the requirements of polyol polyethers for rigid polyurethane foam production. The further increase in the lignin content leads to the appearance of the non-liquefied fraction and the undesirable increase in the viscosity of the liquefied part.
Acknowledgments
The financial support from the 7th FP Collaborative project BIOCORE Contract 241566 and the Latvian budget (LSC grant 564/2012) is gratefully acknowledged. W. Teunissen and J.C. van der Puten from WUR-FBR are kindly acknowledged for SEC analysis.
References
Ahvazi, B., Wojciechowicz, O., Ton-That, T.M., Hawari, J. (2011) Preparation of lignopolyols from wheat straw soda lignin. J. Agr. Food Chem. 59:10505–10516.10.1021/jf202452mSearch in Google Scholar
Alexandridis, P., Hatton, T.A. (1995) Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamic, structure, dynamics, and modelling. Colloid. Surface. A 96:1–46.10.1016/0927-7757(94)03028-XSearch in Google Scholar
Arshanitsa, A., Ponomarenko, J., Dizhbite, T., Andersone, A., Gosselink, R.J.A, van der Putten, J., Lauberts, M., Telysheva, G. (2013) Fractionation of technical lignins as a tool for improvement of their antioxidant properties. J. Anal. Appl. Pyrol. 103:78–85.10.1016/j.jaap.2012.12.023Search in Google Scholar
Arshanitsa, A., Paberza, A., Vevere, L., Cabulis, U., Telysheva, G. (2014) Two approaches for introduction of wheat straw lignin into rigid polyurethane foams. AIP Conf. Proc. 1593:388–391.10.1063/1.4873806Search in Google Scholar
Baker, S.M. (1996) Rapid methoxyl analysis of lignins using gas chromatography. Holzforschung 50:573–574.Search in Google Scholar
Brebu, M., Vasile, C. (2010) Thermal degradation of lignin – a review. Cell. Chem. Technol. 44:353–363.Search in Google Scholar
Cateto, C.A., Barreiro, M.F., Rodrigues, A.E., Belgacem, M.N. (2009) Optimization study of lignin oxypropylation in view of the preparation of polyurethane rigid foams. Ind. Eng. Chem. Res. 48:2583–2589.10.1021/ie801251rSearch in Google Scholar
Cui, C., Sadeghifar, H., Sen, S., Argyropoulos, D.S. (2013) Toward thermoplastic lignin polymers. II. Thermal and polymer characteristics of kraft lignin and derivatives. BioResources 8:864–886.10.15376/biores.8.1.864-886Search in Google Scholar
Delmas, G.H., Benjelloun-Mlayah, B., Bigot; Y.L., Delmas, M. (2011) Functionality of wheat straw lignin extracted in organic acid media. J. Appl. Polym. Sci. 121:491–501.10.1002/app.33592Search in Google Scholar
DIN standard (1994) 53765. Testing of plastic and elastomers; thermal analysis; DSC method.Search in Google Scholar
Evtiougina, M., Barros-Timons, A., Cruz-Pinto, J.J., Neto, C.P., Belgacem, M.N., Gandini, A. (2002) Oxypropylation of cork and the use of the ensuing polyols in polyurethane formulations. Biomacromolecules 3:57–62.10.1021/bm010100cSearch in Google Scholar PubMed
Gandini, A., Belgacem, M.N. (2008) Partial or total oxypropylation of natural polymers and the use of the ensuing materials as composites or polyol macromonomers. In: Monomers, Polymers and Composites from Renewable Resources. Eds. Belgacem, M.N., Gandini, A. Elsevier, Oxford, UK. pp. 273–288.10.1016/B978-0-08-045316-3.00012-0Search in Google Scholar
Glasser, W.G., Barnett, C.A., Rials, T.G., Saraf, V.P. (1984) Engineering plastics from lignin. II. Characterization of hydroxyalkyl lignin derivatives. J. Appl. Polym. Sci. 29:1815–1830.10.1002/app.1984.070290533Search in Google Scholar
Gosselink, R.J.A., van Dam, J.E.G., de Jong, E., Scott, E.L., Sanders, J.P.M., Li, J. Gellerstedt, G. (2010) Fractionation, analysis, and PCA modeling of properties of four technical lignins for prediction of their application potential in binders. Holzforschung 64:193–200.10.1515/hf.2010.023Search in Google Scholar
Granata, A., Argyropoulos, D.S. (1995) 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for accurate determination of the uncondensed and condensed phenolic moieties in lignins. J. Agr. Food. Chem. 43:1538–1544.10.1021/jf00054a023Search in Google Scholar
Gray, R.L., Lee, R.E., Sanders, B.M. (1996) Low volatile antioxidants for scorch of polyurethane foams. J. Vinyl Addit. Technol. 2:265–269.10.1002/vnl.10138Search in Google Scholar
Gromova, M., Arshanitca, A., Telysheva, G., Sevastjanova, A. (1993) Ligols – novel hydroxyl-containing multipurpose materials. In: Cellulosic Chemical, Biochemical and Materials Aspects. Eds. Kennedy, J.F., Phillips, G.O., Williams, P.A. Ellis Horwood, NY. pp. 549–553.Search in Google Scholar
Ionescu, M. Chemistry and Technology for Polyurethane. Rapra Technology Ltd., Shawbury-Shrewsbury-Shropshire, UK, 2005.Search in Google Scholar
Kelley, S.S., Glasser, W.G., Ward, T.C. (1989) Effect of soft-segment content on the properties of lignin-based polyurethanes. In: Lignin Properties and Materials. ACS Sym. Ser. American Chemical Society, Washington, DC, 397. pp. 403–413.10.1021/bk-1989-0397.ch031Search in Google Scholar
Lampinen, J. (2011) Bioplastics – trends, markets and application. In: Proceeding of the 3rd International Conference of Biofoams. Capri, Italy. pp. 41–46.Search in Google Scholar
Li, Y., Ragauskas, A.J. (2012) Kraft lignin-based rigid polyurethane foam. J. Wood Chem. Technol. 32:210–224.10.1080/02773813.2011.652795Search in Google Scholar
Nadji, H., Bruzzese, C., Belgacem, M.N., Benaboura, A., Gandini, A. (2005) Oxypropylation of lignins and preparation of rigid polyurethane foams from the ensuing polyols. Macromol. Mater. Eng. 290:1009–1016.10.1002/mame.200500200Search in Google Scholar
Oliveira, W., Glasser, W.G. (1989) Engineering plastics from lignin. XVI. Starlike macromers with propylene oxide. J. Appl. Polym. Sci. 37:3119–3135.10.1002/app.1989.070371105Search in Google Scholar
Saunders, J.H., Frisch, K. Polyurethane Chemistry and Technology, Part I. Interscience Publishers, New York, USA, 1962.Search in Google Scholar
Storz, H., Vorlop, K.D. (2013) Bio-based plastics: status, challenges and trends. Appl. Agric. Forestry Res. 63:321–332.Search in Google Scholar
Wu, L.C.F., Glasser, W.G. (1984) Engineering plastics from lignin. I. Synthesis of hydroxypropyl lignin. J. Appl. Polym. Sci. 29:1112–1123.10.1002/app.1984.070290408Search in Google Scholar
Yoshida, H., Morck, R., Kringstad, K.P. (1987) Fractionation of kraft lignin by successive extraction with organic solvents. II. Thermal properties of kraft lignin fractions. Holzforshung 41:171–176.10.1515/hfsg.1987.41.3.171Search in Google Scholar
Zakis, G.F. Functional Analysis of Lignins and Their Derivatives. TAPPI Press, Atlanta, 1994.Search in Google Scholar
Zhao, X., Liu, D.,Cheng. K. (2009) Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis. Appl. Microbiol. Biotechnol. 82:815–827.10.1007/s00253-009-1883-1Search in Google Scholar
Article note
13th EWLP, Seville, Spain, June 24–27, 2014.
©2015 by De Gruyter
Articles in the same Issue
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
Articles in the same Issue
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
