Abstract
Acetylation of cellulose nanocrystals (CNCs) is one of the most available routes to enhance hydrophobicity of CNCs. This study investigated the impact of CNC allomorphs on the acetylation. CNC samples with different allomorphs (cellulose I, II and III) were prepared and surface modified by acetylation in heterogeneous system. Then, CNCs and acetylated CNCs (ACNCs) were characterized by solid-state CP/MAS 13C NMR spectroscopy, X-ray diffraction, atomic force microscope and thermogravimetric analysis. It was found that all obtained ACNC allomorphs kept their original intact crystal forms and rod-like structure. The degree of substitution of ACNC I was highest and up to 1.98, followed by ACNC III′, and ACNC II′ was lowest which only came to 0.32 after the reaction of 3 h. In the process of acetylation, the crystallinities of CNC allomorphs decreased, in which CNC II dropped least and CNC III dropped most. Both allomorphic transformation and acetylation improved the thermal stability of native CNC I. This comparative study about CNC allomorphs can offer a new sight for their morphologies and internal properties and also guide for applications like composite materials.
Graphical abstract
Similar content being viewed by others
Abbreviations
- CNCs:
-
Cellulose nanocrystals
- CNC I:
-
Cellulose I nanocrystal
- CNC II:
-
Cellulose II nanocrystal
- CNC III:
-
Cellulose III nanocrystal
- ACNC I:
-
Acetylated cellulose I nanocrystal
- ACNC II:
-
Acetylated cellulose II nanocrystal
- ACNC III:
-
Acetylated cellulose III nanocrystal
References
Abe K, Yano H (2011) Formation of hydrogels from cellulose nanofibers. Carbohyd Polym 85:733–737. https://doi.org/10.1016/j.carbpol.2011.03.028
Abitbol T, Kloser E, Gray DG (2013) Estimation of the surface sulfur content of cellulose nanocrystals prepared by sulfuric acid hydrolysis. Cellulose 20:785–794. https://doi.org/10.1007/s10570-013-9871-0
Abraham E, Kam D, Nevo Y, Slattegard R, Rivkin A, Lapidot S, Shoseyov O (2016) Highly modified cellulose nanocrystals and formation of epoxy-CNC nanocomposites. ACS Appl Mater Interfaces 8:28086–28095. https://doi.org/10.1021/acsami.6b09852
Atalla RH, Gast JC, Sindorf DW, Bartuska VJ, Maciel CE (1980) 13C NMR spectra of cellulose polymorphs. J Am Chem Soc 102:3249–3251
Ávila Ramírez JA, Suriano CJ, Cerrutti P, Foresti ML (2014) Surface esterification of cellulose nanofibers by a simple organocatalytic methodology. Carbohyd Polym 114:416–423. https://doi.org/10.1016/j.carbpol.2014.08.020
Ávila Ramírez JA, Fortunati E, Kenny JM, Torre L, Foresti ML (2017) Simple citric acid-catalyzed surface esterification of cellulose nanocrystals. Carbohyd Polym 157:1358–1364. https://doi.org/10.1016/j.carbpol.2016.11.008
Borysiak S (2013) Influence of cellulose polymorphs on the polypropylene crystallization. J Therm Anal Calorim 113:281–289. https://doi.org/10.1007/s10973-013-3109-0
Brito BSL, Pereira FV, Putaux JL, Jean B (2012) Preparation, morphology and structure of cellulose nanocrystals from bamboo fibers. Cellulose 19:1527–1536. https://doi.org/10.1007/s10570-012-9738-9)
Chen X, Chen J, You T, Wang K, Xu F (2015) Effects of polymorphs on dissolution of cellulose in NaOH/urea aqueous solution. Carbohyd Polym 125:85–91. https://doi.org/10.1016/j.carbpol.2015.02.054
Chidambareswaran PK, Sreenivasan S, Patil NB, Lokhande HT, Shukla SR (1978) Fine structural changes in native and mercerized fibrous cellulose brought about by ethylenediamine and methyl alcohol. J Appl Polym Sci 22:3089–3099
Cranston ED, Gray DG (2006) Morphological and optical characterization of polyelectrolyte multilayers incorporating nanocrystalline cellulose. Biomacromol 7:2522–2530
da Silva Perez D, Montanari S, Vignon MR (2003) TEMPO-mediated oxidation of cellulose III. Biomacromol 4:1417–1425
de Souza Lima MM, Borsali R (2004) Rodlike cellulose microcrystals: structure, properties, and applications. Macromol Rapid Commun 25:771–787. https://doi.org/10.1002/marc.200300268
Faria-Tischer PC, Tischer CA, Heux L, Le Denmat S, Picart C, Sierakowski MR, Putaux JL (2015) Preparation of cellulose II and IIII films by allomorphic conversion of bacterial cellulose I pellicles. Mater Sci Eng, C 51:167–173. https://doi.org/10.1016/j.msec.2015.02.025
Flauzino Neto WP, Putaux JL, Mariano M, Ogawa Y, Otaguro H, Pasquini D, Dufresne A (2016) Comprehensive morphological and structural investigation of cellulose I and II nanocrystals prepared by sulphuric acid hydrolysis. RSC Adv 6:76017–76027. https://doi.org/10.1039/c6ra16295a
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4)
Gong J, Li J, Xu J, Xiang Z, Mo L (2017) Research on cellulose nanocrystals produced from cellulose sources with various polymorphs. RSC Adv 7:33486–33493. https://doi.org/10.1039/c7ra06222b
Gong J, Mo L, Li J (2018) A comparative study on the preparation and characterization of cellulose nanocrystals with various polymorphs. Carbohyd Polym 195:18–28. https://doi.org/10.1016/j.carbpol.2018.04.039
Habibi Y, Vignon MR (2008) Optimization of cellouronic acid synthesis by TEMPO-mediated oxidation of cellulose III from sugar beet pulp. Cellulose 15:177–185. https://doi.org/10.1007/s10570-007-9179-z
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals chemistry, self assembly, and applications. Chem Rev 110:3479–3500
Henrique MA et al (2015) Kinetic study of the thermal decomposition of cellulose nanocrystals with different polymorphs, cellulose I and II, extracted from different sources and using different types of acids. Ind Crops Prod 76:128–140. https://doi.org/10.1016/j.indcrop.2015.06.048
Ishikawa A, Okano T, Sugiyama J (1997) Fine structure and tensile properties of ramie fibres in the crystalline form of cellulose I, II, Illl and IVI. Polymer 38:463–468
Jandura P, Riedl B, Kokta BV (2000) Thermal degradation behavior of cellulose fibers partially esteried with some long chain organic acids. Polym Dagrad Stab 70:387–394
Jin E, Guo J, Yang F, Zhu Y, Song J, Jin Y, Rojas OJ (2016) On the polymorphic and morphological changes of cellulose nanocrystals (CNC-I) upon mercerization and conversion to CNC-II. Carbohyd Polym 143:327–335. https://doi.org/10.1016/j.carbpol.2016.01.048
Kim DY, Nishiyama Y, Wada M, Kuga S (2001) High-yield carbonization of cellulose by sulfuric acid impregnation. Cellulose 8:29–33
Kim NH, Imai T, Wada M, Sugiyama J (2006) Molecular directionality in cellulose polymorphs. Biomacromol 7:274–280
Kono H, Erata T, Takai M (2003) Complete assignment of the CPMAS 13C NMR spectrum of cellulose IIII. Macromolecules 36:3589–3592
Langan P, Nishiyama Y, Chanzy H (1999) A revised structure and hydrogen-bonding system in cellulose II from a neutron fiber diffraction analysis. J Am Chem Soc 121:9940–9946
Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromol 2:410–416
Li X, Li J, Gong J, Kuang Y, Mo L, Song T (2018) Cellulose nanocrystals (CNCs) with different crystalline allomorph for oil in water Pickering emulsions. Carbohyd Polym 183:303–310. https://doi.org/10.1016/j.carbpol.2017.12.085
Lin N, Huang J, Chang PR, Feng J, Yu J (2011) Surface acetylation of cellulose nanocrystal and its reinforcing function in poly(lactic acid). Carbohyd Polym 83:1834–1842. https://doi.org/10.1016/j.carbpol.2010.10.047
Morgado DL, Frollini E (2011) Thermal decomposition of mercerized linter cellulose and its acetates obtained from a homogeneous reaction. Polímeros 21:111–117
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose iβ from synchrotron x-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082
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. Cellulose 125:14300–14306
Numata Y, Kono H, Kawano S, Erata T, Takai M (2003) Cross-polarization/magic-angle spinning 13C nuclear magnetic resonance study of cellulose I–ethylenediamine complex. J Biosci Bioeng 96:461–466. https://doi.org/10.1016/s1389-1723(03)70132-7
Okano T, Sarko A (1985) Mercerization of cellulose. II. Alkali-cellulose intermediates and a possible mercerization mechanism. J Appl Polym Sci 30:325–332
Peng SX, Chang H, Kumar S, Moon RJ, Youngblood JP (2016) A comparative guide to controlled hydrophobization of cellulose nanocrystals via surface esterification. Cellulose 23:1825–1846. https://doi.org/10.1007/s10570-016-0912-3
Qin L, Li WC, Zhu JQ, Liang JN, Li BZ, Yuan YJ (2015) Ethylenediamine pretreatment changes cellulose allomorph and lignin structure of lignocellulose at ambient pressure. Biotechnol Biofuels 8:174–188. https://doi.org/10.1186/s13068-015-0359-z
Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromol 5:1671–1677
Siller M, Amer H, Bacher M, Roggenstein W, Rosenau T, Potthast A (2015) Effects of periodate oxidation on cellulose polymorphs. Cellulose 22:2245–2261. https://doi.org/10.1007/s10570-015-0648-5
Tang LR, Huang B, Ou W, Chen XR, Chen YD (2011) Manufacture of cellulose nanocrystals by cation exchange resin-catalyzed hydrolysis of cellulose. Biores Technol 102:10973–10977. https://doi.org/10.1016/j.biortech.2011.09.070
Uschanov P, Johansson LS, Maunu SL, Laine J (2011) Heterogeneous modification of various celluloses with fatty acids. Cellulose 18:393–404. https://doi.org/10.1007/s10570-010-9478-7
Wada M, Chanzy H, Nishiyama Y, Langan P (2004) Cellulose IIII crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 37:8548–8555
Zhao J, Zhao Y, Wang Z, Peng Z (2016) Effect of polymorphs of cellulose nanocrystal on the thermal properties of poly(lactic acid)/cellulose nanocrystal composites. Eur Phys J E 39:118–125. https://doi.org/10.1140/epje/i2016-16118-2
Acknowledgments
The authors acknowledge the support by National Key Research and Development Plan (No. 2017YFB0307902), the National Science and Technology Major Project (Nos. 2014ZX07213001, 2017ZX07402004) and the Special Support Plan for High-Level Talent Cultivation of Guangdong Province (No. 2014TQ01N603)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wu, Z., Xu, J., Gong, J. et al. Preparation, characterization and acetylation of cellulose nanocrystal allomorphs. Cellulose 25, 4905–4918 (2018). https://doi.org/10.1007/s10570-018-1937-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-1937-6