WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone

Tiina Laaksonen; Jussi K.J. Helminen; Laura Lemetti; Jesper Långbacka; Daniel Rico del Cerro; Michael Hummel; Ilari Filpponen; Antti H. Rantamäki; Tia Kakko; Marianna L. Kemell; Susanne K. Wiedmer; Sami Heikkinen; Ilkka Kilpeläinen; Alistair W.T. King

doi:10.1002/cssc.201701344

WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone

Tiina Laaksonen
, Jussi K.J. Helminen
, Laura Lemetti
, Jesper Långbacka
, Daniel Rico del Cerro
, Michael Hummel
, Ilari Filpponen^*
, Antti H. Rantamäki
, Tia Kakko
, Marianna L. Kemell
, Susanne K. Wiedmer
, Sami Heikkinen
, Ilkka Kilpeläinen
, Alistair W.T. King

^*Corresponding author for this work

Not published at VTT

University of Helsinki
Aalto University
Auburn University

Research output: Contribution to journal › Article › Scientific › peer-review

13 Citations (Scopus)

Abstract

Ionic liquids are used to dewater a suspension of birch Kraft pulp cellulose nanofibrils (CNF) and as a medium for water-free topochemical modification of the nanocellulose (a process denoted as “WtF-Nano”). Acetylation was applied as a model reaction to investigate the degree of modification and scope of effective ionic liquid structures. Little difference in reactivity was observed when water was removed, after introduction of an ionic liquid or molecular co-solvent. However, the viscoelastic properties of the CNF suspended in two ionic liquids show that the more basic, but non-dissolving ionic liquid, allows for better solvation of the CNF. Vibrio fischeri bacterial tests show that all ionic liquids in this study were harmless. Scanning electron microscopy and wide-angle X-ray scattering on regenerated samples show that the acetylated CNF is still in a fibrillar form. 1 D and 2 D NMR analyses, after direct dissolution in a novel ionic liquid electrolyte solution, indicate that both cellulose and residual xylan on the surface of the nanofibrils reacts to give acetate esters.

Original language	English
Pages (from-to)	4879-4890
Number of pages	12
Journal	ChemSusChem
Volume	10
Issue number	24
DOIs	https://doi.org/10.1002/cssc.201701344
Publication status	Published - 22 Dec 2017
MoE publication type	A1 Journal article-refereed

Funding

We would like to acknowledge our funding partner, CLIC Innovation, for support on the general topic of biomass processing with ionic liquids. We would like to acknowledge the Academy of Finland for funding under the projects “WTF-Click-Nano” (311255) and “ILBioMem” (266342). We would also like to acknowledge Prof. Ville Alopaeus (Aalto University) for discussions regarding the very rough calculation of process costs for evaporation of water.

Keywords

acetylation
cellulose
ionic liquids
nanofibers
topochemistry

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10.1002/cssc.201701344

Cite this

Laaksonen, T., Helminen, J. K. J., Lemetti, L., Långbacka, J., Rico del Cerro, D., Hummel, M., Filpponen, I., Rantamäki, A. H., Kakko, T., Kemell, M. L., Wiedmer, S. K., Heikkinen, S., Kilpeläinen, I., & King, A. W. T. (2017). WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone. ChemSusChem, 10(24), 4879-4890. https://doi.org/10.1002/cssc.201701344

@article{45450178efaa430abb5e20f54c2ce462,

title = "WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone",

abstract = "Ionic liquids are used to dewater a suspension of birch Kraft pulp cellulose nanofibrils (CNF) and as a medium for water-free topochemical modification of the nanocellulose (a process denoted as “WtF-Nano”). Acetylation was applied as a model reaction to investigate the degree of modification and scope of effective ionic liquid structures. Little difference in reactivity was observed when water was removed, after introduction of an ionic liquid or molecular co-solvent. However, the viscoelastic properties of the CNF suspended in two ionic liquids show that the more basic, but non-dissolving ionic liquid, allows for better solvation of the CNF. Vibrio fischeri bacterial tests show that all ionic liquids in this study were harmless. Scanning electron microscopy and wide-angle X-ray scattering on regenerated samples show that the acetylated CNF is still in a fibrillar form. 1 D and 2 D NMR analyses, after direct dissolution in a novel ionic liquid electrolyte solution, indicate that both cellulose and residual xylan on the surface of the nanofibrils reacts to give acetate esters.",

keywords = "acetylation, cellulose, ionic liquids, nanofibers, topochemistry",

author = "Tiina Laaksonen and Helminen, \{Jussi K.J.\} and Laura Lemetti and Jesper L{\aa}ngbacka and \{Rico del Cerro\}, Daniel and Michael Hummel and Ilari Filpponen and Rantam{\"a}ki, \{Antti H.\} and Tia Kakko and Kemell, \{Marianna L.\} and Wiedmer, \{Susanne K.\} and Sami Heikkinen and Ilkka Kilpel{\"a}inen and King, \{Alistair W.T.\}",

note = "Funding Information: We would like to acknowledge our funding partner, CLIC Innovation, for support on the general topic of biomass processing with ionic liquids. We would like to acknowledge the Academy of Finland for funding under the projects “WTF-Click-Nano” (311255) and “ILBioMem” (266342). We would also like to acknowledge Prof. Ville Alopaeus (Aalto University) for discussions regarding the very rough calculation of process costs for evaporation of water. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = dec,

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doi = "10.1002/cssc.201701344",

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Laaksonen, T, Helminen, JKJ, Lemetti, L, Långbacka, J, Rico del Cerro, D, Hummel, M, Filpponen, I, Rantamäki, AH, Kakko, T, Kemell, ML, Wiedmer, SK, Heikkinen, S, Kilpeläinen, I & King, AWT 2017, 'WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone', ChemSusChem, vol. 10, no. 24, pp. 4879-4890. https://doi.org/10.1002/cssc.201701344

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T2 - One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone

AU - Laaksonen, Tiina

AU - Helminen, Jussi K.J.

AU - Lemetti, Laura

AU - Långbacka, Jesper

AU - Rico del Cerro, Daniel

AU - Hummel, Michael

AU - Filpponen, Ilari

AU - Rantamäki, Antti H.

AU - Kakko, Tia

AU - Kemell, Marianna L.

AU - Wiedmer, Susanne K.

AU - Heikkinen, Sami

AU - Kilpeläinen, Ilkka

AU - King, Alistair W.T.

N1 - Funding Information: We would like to acknowledge our funding partner, CLIC Innovation, for support on the general topic of biomass processing with ionic liquids. We would like to acknowledge the Academy of Finland for funding under the projects “WTF-Click-Nano” (311255) and “ILBioMem” (266342). We would also like to acknowledge Prof. Ville Alopaeus (Aalto University) for discussions regarding the very rough calculation of process costs for evaporation of water. Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/12/22

Y1 - 2017/12/22

N2 - Ionic liquids are used to dewater a suspension of birch Kraft pulp cellulose nanofibrils (CNF) and as a medium for water-free topochemical modification of the nanocellulose (a process denoted as “WtF-Nano”). Acetylation was applied as a model reaction to investigate the degree of modification and scope of effective ionic liquid structures. Little difference in reactivity was observed when water was removed, after introduction of an ionic liquid or molecular co-solvent. However, the viscoelastic properties of the CNF suspended in two ionic liquids show that the more basic, but non-dissolving ionic liquid, allows for better solvation of the CNF. Vibrio fischeri bacterial tests show that all ionic liquids in this study were harmless. Scanning electron microscopy and wide-angle X-ray scattering on regenerated samples show that the acetylated CNF is still in a fibrillar form. 1 D and 2 D NMR analyses, after direct dissolution in a novel ionic liquid electrolyte solution, indicate that both cellulose and residual xylan on the surface of the nanofibrils reacts to give acetate esters.

AB - Ionic liquids are used to dewater a suspension of birch Kraft pulp cellulose nanofibrils (CNF) and as a medium for water-free topochemical modification of the nanocellulose (a process denoted as “WtF-Nano”). Acetylation was applied as a model reaction to investigate the degree of modification and scope of effective ionic liquid structures. Little difference in reactivity was observed when water was removed, after introduction of an ionic liquid or molecular co-solvent. However, the viscoelastic properties of the CNF suspended in two ionic liquids show that the more basic, but non-dissolving ionic liquid, allows for better solvation of the CNF. Vibrio fischeri bacterial tests show that all ionic liquids in this study were harmless. Scanning electron microscopy and wide-angle X-ray scattering on regenerated samples show that the acetylated CNF is still in a fibrillar form. 1 D and 2 D NMR analyses, after direct dissolution in a novel ionic liquid electrolyte solution, indicate that both cellulose and residual xylan on the surface of the nanofibrils reacts to give acetate esters.

KW - acetylation

KW - cellulose

KW - ionic liquids

KW - nanofibers

KW - topochemistry

UR - https://www.scopus.com/pages/publications/85034957437

U2 - 10.1002/cssc.201701344

DO - 10.1002/cssc.201701344

M3 - Article

C2 - 29112334

AN - SCOPUS:85034957437

SN - 1864-5631

VL - 10

SP - 4879

EP - 4890

JO - ChemSusChem

JF - ChemSusChem

IS - 24

ER -

WtF-Nano: One-Pot Dewatering and Water-Free Topochemical Modification of Nanocellulose in Ionic Liquids or Γ-Valerolactone

Abstract

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Keywords

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