Abstract
A commercial dissolving pulp was treated with aqueous solutions containing 3, 5 and 7 % of an organometalic complex (nitren) with the aim to selectively extract xylan and study its impact on the conventional physical–chemical properties of the pulp. The influence of these treatments on the pulp dissolution in a moderate solvent (8 % NaOH aqueous solution) was assessed by measuring the dissolution yields and the dissolution mechanisms. The results of this study show that nitren treatment has the effect of removing a large part of the xylan present in a dissolving pulp. It is also removing mannans and most important, it is influencing cellulose in two ways, (1) extracting it with more intensity when the nitren concentration increases, and (2) decreasing its mean molecular mass, also more evident with nitren concentration increase. The nitren extractions are favourable for the dissolution in cold NaOH–water, being more effective with higher concentrations. This chemical modification of the fiber surface leads to the disassembly of the primary wall. This allows an easier access of the NaOH reagent to regions not accessible on the initial fibres, which with the decrease of the cellulose molecular weight allows an easier dissolution and gives different dissolution mechanisms.
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References
Boerstel H, Maatman H, Westerink JB, Koenders BM (2001) Liquid crystalline solutions of cellulose in phosphoric acid. Polymer 42:7371–7379
British Celanese (1925) GB 263810
Cai J, Zang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH: urea aqueous solutions. Macromol Biosci 5:539–548
Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H, Han C, Kuga S (2008) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41:9345–9351
Ciechańska D, Gallas E, Struszczyk H (1996) Biotransformation of cellulose. Fibers Text East Eur 1(15):148
Copur Y, Makkonen H (2007) Precision and accuracy studies with Kajaani fiber length analyzers. J Appl Sci 7–7:1043–1047
Cross CF, Bevan EJ, Beadle C (1892) British Patent 8700
Cuissinat C, Navard P (2006a) Swelling and dissolution of cellulose, Part I: free floating cotton and wood fibers in N-methylmorpholine-N-oxide-water mixtures. Macromol Symp 244:1–18
Cuissinat C, Navard P (2006b) Swelling and dissolution of cellulose, Part II: free floating cotton and wood fibers in NaOH water-additives systems. Macromol Symp 244:19–30
Davidson GF (1934) The dissolution of chemically modified cotton cellulose in alkaline solutions. Part 1: in solutions of NaOH, particularly at T C below the normal. J Text I 25:174–196
Davidson GF (1936) The dissolution of chemically modified cotton cellulose in alkaline solutions. Part 2: a comparison of the solvent action of solutions of Lithium, Sodium, Potassium and tetramethylammonium hydroxides. J Text I 27:112–130
Davidson GF (1937) The dissolution of chemically modified cotton cellulose in alkaline solutions. Part 3: in solutions of sodium and potassium hydroxide containing dissolved zinc, beryllium and aluminum oxides. J Text I 28–2:27–44
Egal M (2006) Structure and properties of cellulose/NaOH aqueous solutions, gels and regenerated objects. PhD thesis, Ecole des Mines de Paris/Cemef
Egal M, Budtova T, Navard P (2007) Structure of aqueous solutions of microcrystalline cellulose/sodium hydroxide below 0 C and the limit of cellulose dissolution. Biomacromolecules 8:2282–2287
Egal M, Budtova T, Navard P (2008) The dissolution of microcrystalline cellulose in sodium hydroxide-urea aqueous solutions. Cellulose 15:361–370
Feng L, Chen ZL (2008) Research progress on dissolution and functional modification of cellulose in ionic liquids. J Mol Liq 142:1–5
Fink H-P, Weigel P, Purz H-J (1998) Formation of lyocell-type fibers with skin-core structure. Lenz Ber 78:41–44
Fink H-P, Weigel P, Purz HJ, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Progr Polym Sci 26–9:1473–1524
Firgo H, Eibl K, Kalt W, Meister G (1994) Kritishe fragen zur zukunft der NMMO-technologie. Lenz Ber 9:81–90
Franks NA, Varga JK (1979) Process for making precipitated cellulose. US Patent 4,145,532
Gavillon R, Budtova T (2007) Kinetics of cellulose regeneration from cellulose-NaOH-water gels and comparison with cellulose-N-methylmorpholine–N-oxyde-water solutions. Biomacromolecules 8:424–432
Gavillon R, Budtova T (2008) Aerocellulose: new highly porous cellulose prepared from cellulose-NaOH aqueous solutions. Biomacromolecules 9:269–277
Graenacher C (1934) Cellulose solution, US patent 1,943,176, 9 January 1934
Graenacher C, Sallman R (1939) Cellulose solutions. US Patent 2,179,181
Harrison W (1928) Manufacture of carbohydrate derivatives. US Patent 1,684,732
Hill JW, Jacobsen RA (1938) US patent 2,134,825
Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319
Janzon R, Puls J, Saake B (2006) Upgrading of paper-grade pulps to dissolving pulps by nitren extraction: optimisation of extraction parameters and application to different pulps. Holzforschung 60–4:347–354
Janzon R, Saake B, Puls J (2008a) Upgrading of paper-grade pulps to dissolving pulps by nitren extraction: properties of nitren extracted xylans in comparison to NaOH and KOH extracted xylans. Cellulose 15–1:161–175
Janzon R, Puls J, Bohn A, Potthast A, Saake B (2008b) Upgrading of paper grade pulps to dissolving pulps by nitren extraction: yields, molecular and supramolecular structures of nitren extracted pulps. Cellulose 15–5:739–750
Johnson DL (1969) Compounds dissolved in cyclic amine oxides. US Patent 3,447,939
Kamide K, Okajima K, Matsui T, Kowsaka K (1984) Study on the solubility of cellulose in aqueous alkali solution by deuteration IR and 13C NMR. Polym J 16–12:857–866
Kamide K, Yasuda K, Matsui T, Okajima K, Yamashiki T (1990) Structural change in alkali-soluble cellulose solid during its dissolution into alkaline solutions. Cell Chem Technol 24:23–31
Kamide K, Okajima K, Kowsaka K (1992) Dissolution of natural cellulose into aqueous alkali solution: role of super-molecular structure of cellulose. Polym J 24–1:71–96
Kettenbach G, Stein A (2007) Method for separating hemicelluloses from a biomass containing hemicelluloses and biomass and hemicelluloses obtained by said method US patent 7,198,695, assigned to Rhodia Acetow GmbH, Germany
Kosan B, Michels C, Meister F (2008) Dissolution and forming of cellulose with ionic liquids. Cellulose 15:59–66
Kunze J, Fink HP (2005) Structural changes and activation of cellulose by caustic soda solution with urea. Macromol Symp 223:175–187
Laszkiewicz B (1998) Solubility of bacterial cellulose and its structural properties. J Appl Polym Sci 67:1871–1876
Laszkiewicz B, Cuculo JA (1993) Solubility of cellulose III in sodium hydroxide solution. J Appl Polym Sci 50:27–34
Laszkiewicz B, Wcislo P (1990) Sodium cellulose formation by activation process. J Appl Polym Sci 39:415–425
LeMoigne N, Navard P (2010) Dissolution mechanisms of wood cellulose fibers in NaOH-water. Cellulose 17:31–45
LeMoigne N, Jardeby K, Navard P (2010) Structural changes and alkaline solubility of wood cellulose fibers after enzymatic peeling treatment. Carbohydr Polym 79(2):325–332
Liebert TF (2010) Cellulose solvents-remarkable history, bright future. In: Liebert TF, Heinze TJ, Edgar KJ (eds) Cellulose solvents: for analysis, shaping and chemical modification, ACS symposium series 1033. Oxford Press University, Oxford, pp 3–54
Lin C-X, Zhan H-Y, Liu M-H, Fu S-Y, Lucia LA (2009) Novel preparation and characterisation of cellulose microparticles functionalised in ionic liquids. Langmuir 25:10116–10120
Liu W, Budtova T, Navard P (2011) Influence of ZnO on the properties of dilute and semi-dilute cellulose-NaOH-water solutions. Cellulose 18:911–920
Lu A, Liu Y, Zhang L, Potthast A (2011) Investigation on metastable solution of cellulose dissolved in NaOH/urea aqueous system at low temperature. J Phys Chem B 115:12801–12808
Lue A, Liu Y, Zhang L, Potthast A (2011) Light scattering study on the dynamic behaviour of cellulose inclusion complex in LiOH/urea aqueous solution. Polymer 52:3857–3864
McCorsley III CC, Varga JK (1979) A process for making a precursor of a solution of cellulose. US 4142913
Navard P, Wendler F, Meister F, Bercea M, Budtova T (2013) Preparation and properties of cellulose solutions In: Navard P (Ed) The European polysaccharide network of excellence (EPNOE). Research initiatives and results, Chap. 4
Northolt MG, Boerstel H, Maatman H, Huisman R, Veurink J, Elzerman H (2001) The structure and properties of cellulose fibers spun from an anisotropic phosphoric acid solution. Polymer 42:8249–8264
Östberg L (2012) The influence of the hemicellulose content in dissolving pulps on the gamma number of viscose dopes. In Some aspects on pulp pre-treatment prior to viscose preparation. Licentiate thesis. Faculty of Technology and Science, Chemical Engineering, Karlstad University, Sweden. Karstad Studies 2012:23. ISBN 978-91-7063-427-7
Puls J, Janzon R, Saake B (2006) Comparative removal of hemicelluloses from paper pulps using nitren, cuen, NAOH and KOH. Lenz Ber 86:63–70
Qi H, Chang C, Zhang L (2008) Effects of temperature and molecular weight on dissolution of cellulose in NaOH/urea aqueous solutions. Cellulose 15:779–787
Röhrling J, Potthast A, Rosenau T, Langue T, Ebner G, Sixta H, Kosma P (2002) A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. 1. Method development. Biomacromolecules 33–5:959–968
Rosenau T, Potthast A, Sixta H, Kosma P (2001) The chemistry of side reactions and by-product formation in the system NMMO/cellulose (Lyocell process). Prog Polym Sci 26:1763–1837
Roy C, Budtova T, Navard P, Bedue O (2001) Structure of cellulose-soda solutions at low temperatures. Biomacromolecules 2:687–693
Roy C, Budtova T, Navard P (2003) Rheological properties and gelation of aqueous cellulose-NaOH solutions. Biomacromolecules 4:259–264
Sescousse R, Budtova T (2009) Influence of processing parameters on regeneration kinetics and morphology of porous cellulose from cellulose-NaOH-water solutions. Cellulose 16:417–426
Sescousse R, Gavillon R, Budtova T (2011a) Aerocellulose from cellulose-ionic liquid solutions: preparation, properties and comparison with cellulose-NaOH and cellulose-NMMO routes. Carbohyd Polym 83:1766–1774
Sescousse R, Gavillon R, Budtova T (2011b) Wet and dry highly porous cellulose beads from cellulose-NaOH-water solutions: influence of the preparation conditions on beads shape and encapsulation of inorganic particles. J Mater Sci 46:759–765
Sixta H (2006) Pulp properties and applications. In: Sixta H (ed) Handbook of pulp. Wiley-VCH Verlag GmbH &Co, Weinheim, pp 1009–1068
Sobue H, Kiessig H, Hess K (1939) The cellulose-sodium hydroxide-water system as a function of the temperature. Z Physik Chem B 43:309–328
Spinu M, Dos Santos N, Le Moigne N, Navard P (2011) How does the never-dried state influence the swelling and dissolution of cellulose fibres in aqueous solvent? Cellulose 18:247–256
Sprague BS, Noether HD (1961) The relationship of fine structure to mechanical properties of stretched saponified acetate fibers. Text Res J 31:858–865
Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975
Tsioptsias C, Stefopoulos A, Kokkinomalis I, Papadopoulou L, Panayiotou C (2008) Development of micro- and nano-porous composite materials by processing of cellulose with ionic liquids and supercritical CO2. Green Chem 10:965–971
Turbak AF, Hammer RB, Davies RE, Hergert HL (1980) Cellulose solvents. ChemTech 10:51–57
Turner MB, Spear SK, Holbrey JD, Rogers RD (2004) Production of bioactive cellulose films reconstituted from ionic liquids. Biomacromolecules 5:1379–1384
Vehviläinen M, Kamppuri T, Rom M, Janicki J, Ciechanska D, Grönqvist S, Sioika-Aho M, Christoffersson K, Nousiainen P (2008) Effect of wet spinning parameters on the properties of novel cellulosic fibers. Cellulose 15:671–680
Warwicker JO, Jeffries R, Colbran RL, Robinson RN (1966) A review of the literature on the effect of caustic soda and other swelling agents on the fine structure of cotton. St Ann’s Press, Shirley Institute, Pamphlet, Manchester, p 93
Wawro D, Stęplewski W, Bodek A (2009) Manufacture of cellulose fibers from alkaline solutions of hydrothermally-treated cellulose pulp. Fibers Text East Eur 17:18–22
Willfor S, Pranovich A, Tamminen T, Puls J, Laine C, Suurnakki A, Saake B, Uotila K, Simolin H, Hemming J, Holmbom B (2009) Carbohydrate analysis of plant materials with uronic acid-containing polysaccharides-A comparison between different hydrolysis and subsequent chromatographic analytical techniques. Ind Crop Prod 29:571–580
Yamane C, Saito M, Okajima K (1996) Industrial preparation method of cellulose-alkali dope with high solubility. Sen’I Gakkaaishi 52–6:310–317
Yamashiki T, Kamide K, Okajima K, Kowsaka K, Matsui T, Fukase H (1988) Some characteristic features of dilute aqueous alkali solutions of specific alkali concentration (2.5 mol l-1) which possess maximum solubility power against cellulose. Polym J 20–6:447–457
Zhang H, Wu J, Zhang J, He J (2005) 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 38:8272–8277
Zhao Q, Yam RCM, Zhang B, Yang Y, Cheng X, Li RKY (2009) Novel all-cellulose ecocomposites prepared in ionic liquids. Cellulose 16:217–226
Zhou J, Zhang L (2000) Solubility of cellulose in NaOH/Urea aqueous solution. Polym J 32–10:866–870
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The authors are grateful to Viskase (France and USA), Spontex (France), Sappi (South Africa), Tembec (France and Canada) and Lenzing (Austria) for having supported this project.
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Instiutions are the members of the European Polysaccharide Network of Excellence (www.epnoe.eu).
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Santos, N.M., Puls, J., Saake, B. et al. Effects of nitren extraction on a dissolving pulp and influence on cellulose dissolution in NaOH–water. Cellulose 20, 2013–2026 (2013). https://doi.org/10.1007/s10570-013-9971-x
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DOI: https://doi.org/10.1007/s10570-013-9971-x