Abstract
Esterification of wood with maleic anhydride assists its mechanical fibrillation to realize ultrathin lignocellulose nanofibers (LCNFs) with thicknesses of 3 nm. We investigated the effects of the moisture content of raw wood and the esterification reaction time on the properties of the LCNFs. Increasing the moisture content of raw wood decreases both the amount of maleic acid ester and the lignin content in esterified wood. Moisture is required not only for a high degree of esterification but also for the removal of lignin to prepare ultrathin LCNFs suitable for mechanical fibrillation. 2D HSQC-NMR analysis reveals that cellulose, hemicellulose, and lignin are esterified. The maleic acid ester introduced on the LCNF surface tends to be hydrolyzed, resulting in the detachment of the maleic acid ester. Ester hydrolysis, which is facilitated under alkaline and high temperature conditions, converts the LCNF suspension into a gel. Finally, the stability against ultra violet (UV) light irradiation is examined. Since lignin absorbs UV light, the reduction in the viscosity of the LCNF suspension is lower than that of the pure cellulose nanofiber suspension. These results should contribute to the effective utilization of wood, which is the most abundant biomass.
Similar content being viewed by others
References
Ando D, Nakatsubo F, Yano H (2017) Acetylation of ground pulp: monitoring acetylation via HSQC-NMR spectroscopy. ACS Sustain Chem Eng 5:1755–1762. https://doi.org/10.1021/acssuschemeng.6b02518
Azizi Samir MAS, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromol 6:612–626. https://doi.org/10.1021/bm0493685
Isogai A (2018) Development of completely dispersed cellulose nanofibers. Proc Jpn Acad Ser B Phys Biol Sci 94:161–179. https://doi.org/10.2183/pjab.94.012
Iwamoto S, Endo T (2015) 3 nm Thick lignocellulose nano fibers obtained from esterified wood with maleic anhydride. ACS Macro Lett 4:80–83. https://doi.org/10.1021/mz500787p
Iwamoto S, Kai W, Isogai A, Iwata T (2009) Elastic modulus of single cellulose microfibrils from tunicate measured by atomic force microscopy. Biomacromol 10:2571–2576. https://doi.org/10.1021/bm900520n
Kim H, Ralph J (2014) A gel-state 2D-NMR method for plant cell wall profiling and analysis: a model study with the amorphous cellulose and xylan from ball-milled cotton linters. RSC Adv 4:7549–7560. https://doi.org/10.1039/c3ra46338a
Matsuda H (1987) Preparation and utilization of esterified woods bearing carboxyl groups. Wood Sci Technol 21:75–88. https://doi.org/10.1007/BF00349719
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306. https://doi.org/10.1021/ja037055w
Nishiyama Y, Johnson GP, French AD, Forsyth VT, Langan P (2008) Neutron crystallography, molecular dynamics, and quantum mechanics studies of the nature of hydrogen bonding in cellulose Iβ. Biomacromol 9:3133–3140. https://doi.org/10.1021/bm800726v
Noguchi Y, Homma I, Matsubara Y (2017) Complete nanofibrillation of cellulose prepared by phosphorylation. Cellulose 24:1295–1305. https://doi.org/10.1007/s10570-017-1191-3
Pandey KK, Vuorinen T (2008) Comparative study of photodegradation of wood by a UV laser and a xenon light source. Polym Degrad Stab 93:2138–2146. https://doi.org/10.1016/j.polymdegradstab.2008.08.013
Podschun J, Stücker A, Saake B, Lehnen R (2015) Structure-function relationships in the phenolation of lignins from different sources. ACS Sustain Chem Eng 3:2526–2532. https://doi.org/10.1021/acssuschemeng.5b00705
Qu C, Kishimoto T, Kishino M, Hamada M, Nakajima N (2011) Heteronuclear single-quantum coherence nuclear magnetic resonance (HSQC NMR) characterization of acetylated fir (Abies sachallnensis MAST) wood regenerated from ionic liquid. J Agric Food Chem 59:5382–5389. https://doi.org/10.1021/jf200498n
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromol 8:2485–2491. https://doi.org/10.1021/bm0703970
Saito T, Kuramae R, Wohlert J, Berglund LA, Isogai A (2013) An ultrastrong nanofibrillar biomaterial: the strength of single cellulose nanofibrils revealed via sonication-induced fragmentation. Biomacromol 14:248–253. https://doi.org/10.1021/bm301674e
Saito Y, Endo T, Ando D, Nakatsubo F, Yano H (2018) Influence of drying process on reactivity of cellulose and xylan in acetylation of willow (Salix schwerinii E. L. Wolf) kraft pulp monitored by HSQC-NMR spectroscopy. Cellulose 25:6319–6331. https://doi.org/10.1007/s10570-018-2034-6
Sehaqui H, Kulasinski K, Pfenninger N, Zimmermann T, Tingaut P (2017) Highly carboxylated cellulose nanofibers via succinic anhydride esterification of wheat fibers and facile mechanical disintegration. Biomacromol 18:242–248. https://doi.org/10.1021/acs.biomac.6b01548
Shimizu M, Saito T, Nishiyama Y, Iwamoto S, Yano H, Isogai A, Endo T (2016) Fast and robust nanocellulose width estimation using turbidimetry. Macromol Rapid Commun 37:1581–1586. https://doi.org/10.1002/marc.201600357
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2012) Determination of structural carbohydrates and lignin in biomass. NREL Tech Rep NREL/TP-510-42618
Wada M (2002) Lateral thermal expansion of cellulose Iβ and III(I) polymorphs. J Polym Sci B Polym Phys 40:1095–1102. https://doi.org/10.1002/polb.10166
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Iwamoto, S., Saito, Y., Yagishita, T. et al. Role of moisture in esterification of wood and stability study of ultrathin lignocellulose nanofibers. Cellulose 26, 4721–4729 (2019). https://doi.org/10.1007/s10570-019-02408-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-019-02408-x