Cellulose

, Volume 25, Issue 7, pp 3873–3883 | Cite as

Optimization of carboxymethylation reaction as a pretreatment for production of cellulose nanofibrils

  • Wanhee Im
  • Seakho Lee
  • Araz Rajabi Abhari
  • Hye Jung Youn
  • Hak Lae Lee
Original Paper
  • 18 Downloads

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.

Keywords

Cellulose nanofibrils Carboxymethylation Carboxyl content Chemical cost saving 

Notes

Acknowledgments

This work was supported by the Technological Innovation Program funded by the Ministry of Trade, Industry & Energy (10062717).

References

  1. 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 CrossRefGoogle Scholar
  2. 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):1918–1932Google Scholar
  3. 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 CrossRefGoogle Scholar
  4. 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 CrossRefGoogle Scholar
  5. 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 CrossRefGoogle Scholar
  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 CrossRefGoogle Scholar
  7. 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 CrossRefGoogle Scholar
  8. 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 CrossRefGoogle Scholar
  9. 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 CrossRefGoogle Scholar
  10. 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 CrossRefGoogle Scholar
  11. 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 CrossRefGoogle Scholar
  12. 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 CrossRefGoogle Scholar
  13. 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 Google Scholar
  14. 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 CrossRefGoogle Scholar
  15. Klemm D, Philipp B, Heinze T, Hjeinze U (1998) Comprehensive cellulose chemistry. Wiley-VCH, New YorkCrossRefGoogle Scholar
  16. 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 CrossRefGoogle Scholar
  17. 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 CrossRefGoogle Scholar
  18. 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 CrossRefGoogle Scholar
  19. 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):1988–2003Google Scholar
  20. 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 CrossRefGoogle Scholar
  21. 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 CrossRefGoogle Scholar
  22. 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 CrossRefGoogle Scholar
  23. 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 CrossRefGoogle Scholar
  24. 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 CrossRefGoogle Scholar
  25. 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 CrossRefGoogle Scholar
  26. 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 CrossRefGoogle Scholar
  27. 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 CrossRefGoogle Scholar
  28. 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 CrossRefGoogle Scholar
  29. 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 CrossRefGoogle Scholar
  30. 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 CrossRefGoogle Scholar
  31. 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 CrossRefGoogle Scholar
  32. 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 CrossRefGoogle Scholar
  33. 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 CrossRefGoogle Scholar
  34. 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 CrossRefGoogle Scholar
  35. 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 CrossRefGoogle Scholar
  36. 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 CrossRefGoogle Scholar
  37. 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 CrossRefGoogle Scholar
  38. 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 CrossRefGoogle Scholar
  39. 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 CrossRefGoogle Scholar
  40. 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 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Forest Sciences, Research Institute of Agriculture and Life Sciences, College of Agriculture and Life SciencesSeoul National UniversitySeoulKorea

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