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

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

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Fig. 1

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

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

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

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

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

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Redrawn from (Liu and Baumann 2002)

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

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

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

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

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

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

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Redrawn from (Song et al. 2008b)

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

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

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

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

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

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

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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.

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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

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Keywords

  • Novel cellulose solvents
  • Cellulose dissolution mechanism
  • Homogeneous derivatization
  • Cellulose esters
  • Cellulose ethers