Skip to main content
SpringerLink
Log in

Twenty-five years of cellulose chemistry: innovations in the dissolution of the biopolymer and its transformation into esters and ethers

  • Review Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

The anniversary of the journal “Cellulose” is an opportunity to review innovations that were introduced during the past 25 years. Of these, from our perspective, the development of solvents that dissolve cellulose physically, i.e., without formation of covalent bonds is most relevant. The reasons are that cellulose can be regenerated from these media in different shapes and transformed into many important derivatives. Twenty-five years is a long time-span! As the volume of information on the applications of the above-mentioned solvents in cellulose chemistry is extensive, we made choices to reach a balance between the amount of material covered and the length of the review. Consequently, we focus on cellulose derivatization under homogeneous reaction conditions to produce selected derivatives. We dwell on the latter because a comprehensive discussion was recently published on derivatization under heterogeneous and homogeneous conditions (Heinze et al. in Cellulose derivatives, Springer, Cham, pp 259–292, 2018a). The derivatives selected are esters of organic acids, ionic and nonionic ethers because of their tremendous commercial and scientific importance. Cellulose derivatization in homogeneous media is advantageous because of much better control of product properties relative to those obtained under the heterogeneous counterparts. These properties include degree of substitution in the anhydroglucose unit and along the biopolymer back-bone, and regioselectivity. Thus, novel cellulose derivatives were prepared that are not accessible under heterogeneous conditions. The requirement to dissolve cellulose physically is to disrupt hydrogen bonding and hydrophobic interactions. Thus, the solvents employed to dissolve cellulose are usually composed of strong electrolytes whose cations and anions interact preferentially with cellulose. These electrolytes are used pure or as solutions in water or dipolar aprotic solvents. Salient examples include LiCl/N,N-dimethylacetamide, tetra(n-butyl)ammonium fluoride·3H2O/dimethyl sulfoxide, ionic liquids, salts of quaternary amines and super-bases. We discuss briefly the essentials of each solvent in terms of its mechanism of cellulose dissolution and show the most relevant results regarding its application for obtaining esters and ethers and back the discussion with relevant references. This information is summarized at the end of the review. We hope that this historical perspective shows the innovations made since the first publication of “Cellulose” and points out to future possibilities—with potential industrial application—of this renewable raw material and its biocompatible and biodegradable derivatives.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1

Reprinted with permission from (Pinkert et al. 2010), copyright (2010) American Chemical Society

Fig. 2

Adapted from (Miyamoto et al. 2009), copyright (2009), with permission from Elsevier

Fig. 3

Reprinted (adapted) with permission from (Zhang et al. 2014), copyright (2014) American Chemical Society

Fig. 4

Reprinted (adapted) with permission from (Zhang et al. 2014), copyright (2014) American Chemical Society

Fig. 5

Reprinted by permission from (Heinze et al. 2006), Springer Nature, copyright (2006)

Fig. 6

Reprinted from (Nawaz et al. 2013), copyright (2013), with permission from Elsevier

Fig. 7
Fig. 8

Redrawn from (Liu and Baumann 2002)

Fig. 9
Fig. 10

Reprinted with permission from (Fox et al. 2011), copyright (2011) American Chemical Society

Fig. 11

Reprinted from (Heinze and Liebert 2012), copyright (2012), with permission from Elsevier

Fig. 12

Reprinted with permission from Östlund et al. (2009), copyright (2009) American Chemical Society

Fig. 13
Fig. 14

Reprinted with permission from Köhler and Heinze (2007), copyright (2007), with permission from Elsevier

Fig. 15

Reprinted from (Luo and Zhang 2013), copyright (2013), with permission from Elsevier

Fig. 16

Reproduced from Ref. (Wang et al. 2018), with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry

Fig. 17

Reprinted with permission from Zhong et al. (2017), copyright (2017), with permission from Elsevier

Fig. 18

Redrawn from (Song et al. 2008b)

Fig. 19

Adopted by permission from Heinze et al. (2018d), Springer Nature, copyright (2018)

Fig. 20

Reprinted with permission from Abe et al. (2017), copyright (2017) American Chemical Society

Fig. 21

Reprinted from (Luo and Zhang 2013), copyright (2013), with permission from Elsevier

Fig. 22

Reprinted with permission from Huang et al. (2016), Copyright (2016) American Chemical Society

Fig. 23

Reprinted with permission from Achtel et al. (2018), copyright (2018) WILEY

Fig. 24
Fig. 25

Reprinted and modified with permission from Possidonio et al. (2010), copyright (2010) WILEY

Fig. 26

Reprinted and modified with permission from Köhler et al. (2007), copyright (2007) WILEY

Fig. 27

Reprinted and modified with permission from Lv et al. (2012), copyright (2012), with permission from Elsevier

Fig. 28

Reprinted and modified with permission from Elschner et al. (2014), copyright (2014) WILEY

Similar content being viewed by others

Abbreviations

AcO:

Acetate

AGU:

Anhydroglucose unit

[AlMeIm]Cl:

1-Allyl-3-methylimidazolium chloride

BC:

Bacterial cellulose

[BuMeIm]Cl:

1-(n-Butyl)-3-methylimidazolium chloride

CDI:

Carbonyldiimidazole

CT:

Cellulose tosylate

CHPTMA Cl:

(3-Chloro-2-hydroxypropyl)trimethyl-ammonium chloride

DAS:

Dipolar aprotic solvent

DBN:

1,5-Diazabicyclo[4.3.0]non-5-ene

DBU:

1,8-Diazabicyclo[5.4.0]undec-7-ene

DCC:

N,N′-Dicyclohexylcarbodiimide

DLS:

Dynamic light scattering

DMAc:

N,N-Dimethylacetamide

DMF:

N,N-Dimethylformamide

DMSO:

Dimethyl sulfoxide

DP:

Average degree of polymerization

DS:

Average degree of substitution

EPTMA Cl:

(2,3-Epoxypropyl)trimethylammonium chloride

E T(30):

Solvent empirical polarity parameter (in kcal mol−1) as determined by the solvatochromic probe 2,6-diphenyl-4-(2,4,6-triphenylpyridin-1-ium-1-yl)phenolate

[EtMeIm]AcO:

1-Ethyl-3-methylimidazolium acetate

HEC:

Hydroxyethyl cellulose

HPC:

Hydroxypropyl cellulose

Ic :

Index of crystallinity

IL:

Ionic liquid

ImIL:

Imidazolium based IL

log P:

Partition coefficient of a substance between (mutually saturated) n-octanol and water

MALS:

Multiangle light scattering

MC:

Methyl cellulose

MD:

Molecular dynamic simulations

MM:

Average molar mass5

MS:

Average degree of molar substitution

[N2228]Cl:

Triethyl(n-octyl)ammonium chloride

NMMO:

N-Methylmorpholine-N-oxide

QAE:

Quaternary ammonium electrolyte

SA:

Solvent Lewis acidity

SB:

Solvent Lewis basicity

[TBA]F·3H2O:

Tetra(n-butyl)ammonium fluoride trihydrate

TC:

Trityl cellulose

TsCl:

Tosyl chloride

References

Download references

Acknowledgments

O. A. El Seoud and M. Kostag thank the FAPESP research foundation for financial support and postdoctoral fellowship (Grants 2014/22136-4 and 2016/22869-7, respectively). O. A. El Seoud thanks CNPq for research productivity fellowship (Grant 307022/2014-5). The financial support of the DFG-funded Collaborative Research Centre PolyTarget (SFB 1278, Project A02) is gratefully acknowledged by T. Heinze. We thank Gabriel O. El Seoud for the art work.

Author information

Authors and Affiliations

  1. Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes 748, São Paulo, SP, 05508-000, Brazil

    Marc Kostag & Omar A. El Seoud

  2. Centre of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Humboldtstraße 10, 07743, Jena, Germany

    Martin Gericke & Thomas Heinze

Authors
  1. Marc Kostag
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Martin Gericke
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Thomas Heinze
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Omar A. El Seoud
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Omar A. El Seoud.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kostag, M., Gericke, M., Heinze, T. et al. Twenty-five years of cellulose chemistry: innovations in the dissolution of the biopolymer and its transformation into esters and ethers. Cellulose 26, 139–184 (2019). https://doi.org/10.1007/s10570-018-2198-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-018-2198-0

Keywords

Search

Navigation