Abstract
We investigated the optimal reaction conditions for carboxymethylation as a pretreatment method for the production of cellulose nanofibrils (CNF). The influence of the reaction sequence, solvent composition, and presence of water in the reaction medium on the carboxymethylation of pulp was studied. We also investigated the effects of water in the reaction medium on CNF properties. The most effective carboxymethylation of pulp was achieved with non-solvent exchanged pulp and isopropanol. An increase in pulp consistency increased the carboxyl group content. The optimum reaction condition used only one-third the amounts of monochloroacetic acid and sodium hydroxide for the same level of carboxymethylation. The number of passes required for mechanical fibrillation of the pulp, the morphology and dispersion instability of CNF were all strongly influenced by the carboxyl content introduced during the carboxymethylation reaction. The number of mechanical treatment steps required to produce CNF decreased as the carboxyl content increased. Pulp with a high carboxyl content resulted in a more stable suspension due to the increased electrostatic repulsion between the fibrils.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ahola S, Österberg M, Laine J (2008) Cellulose nanofibrils-adsorption with poly (amideamine) epichlorohydrin studied by QCM-D and application as a paper strength additive. Cellulose 15:303–314. https://doi.org/10.1007/s10570-007-9167-3
Ambjörnsson HA, Schenzel K, Germgård U (2013) Carboxymethyl cellulose produced at different mercerization conditions and characterized by NIR FT Raman spectroscopy in combination with multivariate analytical methods. BioResources 8(2):1918–1932
Aulin C, Netrval J, Wågberg L, Lindström T (2010) Aerogels from nanofibrillated cellulose with tunable oleophobicity. Soft Matter 6:3298–3305. https://doi.org/10.1039/c001939a
Besbes I, Alila S, Boufi S (2011) Nanofibrillated cellulose from TEMPO-oxidized eucalyputs fibres: effect of the carboxyl content. Carbohydr Polym 84:975–983. https://doi.org/10.1016/g.carbpol.2010.12.052
Bhattacharyya D, Singhal RS, Kulkarni PR (1995) A comparative account of conditions for synthesis of sodium carboxymethyl starch from corn and amaranth starch. Carbohydr Polym 27:247–253. https://doi.org/10.1016/0144-8617(95)00083-6
Chen Y, Wan J, Dong X, Ma Y (2013) Fiber properties of eucalyptus kraft pulp with different carboxyl group contents. Cellulose 20:2839–2846. https://doi.org/10.1007/s10570-013-0055-8
Eyholzer C, Bordeanu N, Lopez-Suevos F, Rentsch D, Zimmermann T, Oksman K (2010) Preparation and characterization of water-redispersible nanofibrillated cellulose in powder form. Cellulose 17:19–30. https://doi.org/10.1007/s10570-009-9372-3
Fall AB, Lindström SB, Sundman O, Ödberg L, Wågberg L (2011) Colloidal stability of aqueous nanofibrillated cellulose dispersions. Langmuir 27:11332–11338. https://doi.org/10.1021/la201947x
Fujisawa S, Okita Y, Fukuzumi H, Saito T, Isogai A (2011) Preparation and characterization of TEMPO-oxidized cellulose nanofibril with free carboxyl groups. Carbohydr Polym 84:579–583. https://doi.org/10.1016/j.carbpol.2010.12.029
Fukuzumi H, Tanaka R, Satio T, Isogai A (2014) Dispersion stability and aggregation behavior of TEMPO-oxidized cellulose nanofibrils in water as a function of salt addition. Cellulose 21:1553–1559. https://doi.org/10.1007/s10570-014-0180-z
Ghanadpour M, Carosio F, Larsson PT, Wågberg L (2015) Phosphorylated cellulose nanofibrils: a renewable nanomaterial for the preparation of intrinsically flame-retardant materials. Biomacromolecules 16:3399–3410. https://doi.org/10.1021/acs/biomac.5b01117
Hu L, Zheng G, Yao J, Liu N, Weil B, Eskilsson M, Karabulut E, Ruan Z, Fan S, Bloking JT, McGehee MD, Wågberg L, Cui Y (2013) Transparent and conductive paper from nanocellulose fibers. Energy Environ Sci 6:513–518. https://doi.org/10.1039/c2ee23635d
Im W, Lee S, Park H, Lee HL, Youn HY (2016) Characteristics of cellulose nanofibrils by carboxymethylation pretreatment: effect of the carboxyl contents. J Korea TAPPI 48(6):1–8. https://doi.org/10.7584/JKTAPPI.2016.12.48.6.1
Jie Y, Wen-ren C, Manurung RM, Ganzeveld KJ, Heeres HJ (2004) Exploratory studies on the carboxymethylation of cassava starch in water-miscible organic media. Starch 56:100–107. https://doi.org/10.1002/star.200300239
Klemm D, Philipp B, Heinze T, Hjeinze U (1998) Comprehensive cellulose chemistry. Wiley-VCH, New York
Liimatainen H, Visanko M, Sirviö J, Hormi O, Niinimäki J (2013) Sulfonated cellulose nanofibrils obtained from wood pulp through regioselective oxidative bisulfite pre-treatment. Cellulose 20:741–749. https://doi.org/10.1007/s10570-013-9865-y
Mann G, Kunze J, Loth F, Fink HP (1998) Cellulose ethers with a block-like distribution of the substituents by structure-selective derivatization of cellulose. Polymer 39(14):3155–3165. https://doi.org/10.1016/S0032-3861(97)10006-4
Mansikkamäki P, Lahtinen M, Rissanen K (2005) Structural changes of cellulose crystallites induced by mercerization in different solvent system: determined by powder X-ray diffraction method. Cellulose 12:233–242. https://doi.org/10.1007/s10570-004-3132-1
Mohkami M, Talaeipour M (2011) Investigation of the chemical structure of carboxylated and carboxymethylated fibers from waste paper via XRD and FTIR analysis. BioResources 6(2):1988–2003
Naderi A, Larsson PT, Stevanic JS, Lindström T, Erlandsson J (2017) Effect of the size of the charged group on the properties of alkoxylated NFCs. Cellulose 24(3):1307–1317. https://doi.org/10.1007/s10570-017-1190-4
Onyianta AJ, Dorris M, Williams RL (2018) Aqueous morpholine pre-treatment in cellulose nanofibril(CNF) production: comparison with carboxymethylation and TEMPO oxidization pre-treatment methods. Cellulose 25:1047–1064. https://doi.org/10.1007/s10570-017-1631-0
Qi H, Liebert T, Meister F, Heinze T (2009) Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution. React Funct Polym 69:779–784. https://doi.org/10.1016/j.reactfunctpolym.2009.06.007
Qiu H, He L (1999) Synthesis and properties study of carboxymethyl cassava starch. Polym Adv Technol 10:468–472. https://doi.org/10.1002/(SICI)1099-1581(199907)10:7
Ramos LA, Frollini E, Heinze T (2005) Carboxymethylation of cellulose in the new solvent dimethyl sulfoxide/tetrabutylammonium fluoride. Carbohydr Polym 60:259–267. https://doi.org/10.1016/j.carbpol.2005.01.010
Ren JL, Sun RC, Peng F (2008) Carboxymethylation of hemicelluloses isolated from sugarcane bagasse. Polym Degrad Stab 93:786–793. https://doi.org/10.1016/j.polymdegradstab.2008.01.011
Rodionova G, Lenes M, Eriksen Ø, Gregersen Ø (2011) Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications. Cellulose 18:127–134. https://doi.org/10.1007/s10570-010-9474-y
Saito T, Okita Y, Nge TT, Sugiyama J, Isogai A (2006) TEMPO-mediated oxidation of native cellulose: microscopic analysis of fibrous fractions in the oxidized products. Carbohydr Polym 65:435–440. https://doi.org/10.1016/j.carbpol.2006.01.034
Sim K, Youn HJ (2016) Preparation of porous sheets with high mechanical strength by the addition of cellulose nanofibrils. Cellulose 23:1383–1392. https://doi.org/10.1007/s10570-016-0865-6
Siró I, Plackett D, Hedenqvist M, Ankerfors M, Lindström T (2011) Highly transparent films from carboxymethylated microfibrillated cellulose: the effect of multiple homogenization steps on key properties. J Appl Polym Sci 119:2652–2660. https://doi.org/10.1002/app.32831
Stigsson V, Kloow G, Germgård U (2006) The influence of the solvent system used during manufacturing of CMC. Cellulose 13:705–712. https://doi.org/10.1007/s10570-006-9083-y
Suflet DM, Chitanu GC, Popa VI (2006) Phosphorylation of polysaccharides: new results on synthesis and characterization of phosphorylated cellulose. React Funct Polym 66:1240–1249. https://doi.org/10.1016/j.reactfunctpolym.2006.03.006
Syverud K, Chinaga-Carraso G, Toledo J, Toledo PG (2011) A comparative study of Eucalyptus and Pinus radiate pulp fibres as raw materials for production of cellulose nanofibrils. Carbohydr Polym 84:1003–1038. https://doi.org/10.1016/j.carbpol.2010.12.066
Tijsen CJ, Kolk HJ, Stamhuis EJ, Beenackers AACM (2001) An experimental study on the carboxymethylation of granular potato starch in non-aqueous media. Carbohydr Polym 45:219–226. https://doi.org/10.1016/S0144-8617(00)00243-5
Wågberg L, Decher G, Norgren M, Lindström T, Ankerfors M, Axnäs K (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24(3):784–795. https://doi.org/10.1021/1a70248v
Wang M, Olszewska A, Walther A, Malho JM, Schacher FH, Ruokolainen J, Ankerfors M, Laine J, Berglund LA, Österberg M, Ikkala O (2011) Colloidal ionic assembly between anionic native cellulose nanofibrils and cationic block copolymer micelles into biomimetic nanocomposites. Biomacromolecules 12:2074–2081. https://doi.org/10.1021/bm101561m
Wang QQ, Zhu JY, Gleisner R, Kuster TA, Baxa U, Mcneil SE (2012) Morphological development of cellulose fibrils of a bleached eucalyptus pulp by mechanical fibrillation. Cellulose 19:1631–1643. https://doi.org/10.1007/s10570-012-9745-x
Wiśniewska M (2010) Influences of polyacrylic acid adsorption and temperature on the alumina suspension stability. Powder Technol 198:258–266. https://doi.org/10.1016/j.powtec.2009.11.016
Yokota H (1985) The mechanism of cellulose alkalization in the isopropyl alcohol–water–sodium hydroxide–cellulose system. J Appl Polym Sci 30:263–277. https://doi.org/10.1002/app.1984.070300121
Zhang F, Ren H, Tong G, Deng Y (2016) Ultra-lightweight poly (sodium acrylate) modified TEMPO-oxidized cellulose nanofibrils aerogel spheres and their superabsorbent properties. Cellulose 23:3665–3676. https://doi.org/10.1007/s10570-016-1041-8
Zhou M, Persion M, Sarrazin J (1996) Methanol removal from organic mixtures by pervaporation using polypyrrole membranes. J Membr Sci 117:303–309. https://doi.org/10.1016/0376-7388(96)00091-9c
Acknowledgments
This work was supported by the Technological Innovation Program funded by the Ministry of Trade, Industry & Energy (10062717).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Im, W., Lee, S., Rajabi Abhari, A. et al. Optimization of carboxymethylation reaction as a pretreatment for production of cellulose nanofibrils. Cellulose 25, 3873–3883 (2018). https://doi.org/10.1007/s10570-018-1853-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-1853-9