Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains

Daniela C. Ferreira; Mayara L. Oliveira; Thais A. Bioni; Haq Nawaz; Alistair W.T. King; Ilkka Kilpeläinen; Michael Hummel; Herbert Sixta; Omar A. El Seoud

doi:10.1016/j.carbpol.2019.02.024

Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains

Daniela C. Ferreira
, Mayara L. Oliveira
, Thais A. Bioni
, Haq Nawaz
, Alistair W.T. King
, Ilkka Kilpeläinen
, Michael Hummel
, Herbert Sixta^*
, Omar A. El Seoud

^*Corresponding author for this work

Not published at VTT

Universidade de São Paulo
University of Helsinki
Aalto University
IPT - Institute for Technological Research

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

39 Citations (Scopus)

Abstract

The efficiency of mixtures of ionic liquids (ILs) and molecular solvents in cellulose dissolution and derivatization depends on the structures of both components. We investigated the ILs 1-(1-butyl)-3-methylimidazolium acetate (C ₄ MeImAc) and 1-(2-methoxyethyl)-3-methylimidazolium acetate (C ₃ OMeImAc) and their solutions in dimethyl sulfoxide, DMSO, to assess the effect of presence of an ether linkage in the IL side-chain. Surprisingly, C ₄ MeImAc-DMSO was more efficient than C ₃ OMeImAc-DMSO for the dissolution and acylation of cellulose. We investigated both solvents using rheology, NMR spectroscopy, and solvatochromism. Mixtures of C ₃ OMeImAc-DMSO are more viscous, less basic, and form weaker hydrogen bonds with cellobiose than C ₄ MeImAc-DMSO. We attribute the lower efficiency of C ₃ OMeImAc to “deactivation” of the ether oxygen and C2–H of the imidazolium ring due to intramolecular hydrogen bonding. Using the corresponding ILs with C2–CH ₃ instead of C2–H, namely, 1-butyl-2,3-dimethylimidazolium acetate (C ₄ Me ₂ ImAc) and 1-(2-methoxyethyl)-2,3-dimethylimidazolium acetate (C ₃ OMe ₂ ImAc) increased the concentration of dissolved cellulose; without noticeable effect on biopolymer reactivity.

Original language	English
Pages (from-to)	206-214
Number of pages	9
Journal	Carbohydrate Polymers
Volume	212
DOIs	https://doi.org/10.1016/j.carbpol.2019.02.024
Publication status	Published - 15 May 2019
MoE publication type	A1 Journal article-refereed

Funding

D. C. Ferreira thanks FIPT for PDCE fellowship for her stay at Aalto University. M. L. Oliveira, T. A. Bioni and H. Nawaz thanks FIPT, Capes, and FAPESP, respectively for their fellowships. O. A. El Seoud thanks CNPq for research productivity fellowships (grant 307022/2014-5 ) and FAPESP for financial support ( 2014/22136-4 ). H. Sixta and M. Hummel wish to thank Tekes – the Finnish Funding Agency for Innovation - and Finnish Bioeconomy Cluster FIBIC Ltd for funding.

Keywords

Biopolymer derivatization
Cellulose dissolution
Cellulose esters
Ionic liquid-DMSO
Solvatochromism

Access to Document

10.1016/j.carbpol.2019.02.024

Cite this

@article{d206feac4bf04838b78570d897bbf349,

title = "Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains",

abstract = " The efficiency of mixtures of ionic liquids (ILs) and molecular solvents in cellulose dissolution and derivatization depends on the structures of both components. We investigated the ILs 1-(1-butyl)-3-methylimidazolium acetate (C 4 MeImAc) and 1-(2-methoxyethyl)-3-methylimidazolium acetate (C 3 OMeImAc) and their solutions in dimethyl sulfoxide, DMSO, to assess the effect of presence of an ether linkage in the IL side-chain. Surprisingly, C 4 MeImAc-DMSO was more efficient than C 3 OMeImAc-DMSO for the dissolution and acylation of cellulose. We investigated both solvents using rheology, NMR spectroscopy, and solvatochromism. Mixtures of C 3 OMeImAc-DMSO are more viscous, less basic, and form weaker hydrogen bonds with cellobiose than C 4 MeImAc-DMSO. We attribute the lower efficiency of C 3 OMeImAc to “deactivation” of the ether oxygen and C2–H of the imidazolium ring due to intramolecular hydrogen bonding. Using the corresponding ILs with C2–CH 3 instead of C2–H, namely, 1-butyl-2,3-dimethylimidazolium acetate (C 4 Me 2 ImAc) and 1-(2-methoxyethyl)-2,3-dimethylimidazolium acetate (C 3 OMe 2 ImAc) increased the concentration of dissolved cellulose; without noticeable effect on biopolymer reactivity. ",

keywords = "Biopolymer derivatization, Cellulose dissolution, Cellulose esters, Ionic liquid-DMSO, Solvatochromism",

author = "Ferreira, \{Daniela C.\} and Oliveira, \{Mayara L.\} and Bioni, \{Thais A.\} and Haq Nawaz and King, \{Alistair W.T.\} and Ilkka Kilpel{\"a}inen and Michael Hummel and Herbert Sixta and \{El Seoud\}, \{Omar A.\}",

note = "Funding Information: D. C. Ferreira thanks FIPT for PDCE fellowship for her stay at Aalto University. M. L. Oliveira, T. A. Bioni and H. Nawaz thanks FIPT, Capes, and FAPESP, respectively for their fellowships. O. A. El Seoud thanks CNPq for research productivity fellowships (grant 307022/2014-5 ) and FAPESP for financial support ( 2014/22136-4 ). H. Sixta and M. Hummel wish to thank Tekes – the Finnish Funding Agency for Innovation - and Finnish Bioeconomy Cluster FIBIC Ltd for funding. Publisher Copyright: {\textcopyright} 2019",

year = "2019",

month = may,

day = "15",

doi = "10.1016/j.carbpol.2019.02.024",

language = "English",

volume = "212",

pages = "206--214",

journal = "Carbohydrate Polymers",

issn = "0144-8617",

publisher = "Elsevier",

}

TY - JOUR

T1 - Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose

T2 - Effects of alkyl and alkoxy side chains

AU - Ferreira, Daniela C.

AU - Oliveira, Mayara L.

AU - Bioni, Thais A.

AU - Nawaz, Haq

AU - King, Alistair W.T.

AU - Kilpeläinen, Ilkka

AU - Hummel, Michael

AU - Sixta, Herbert

AU - El Seoud, Omar A.

N1 - Funding Information: D. C. Ferreira thanks FIPT for PDCE fellowship for her stay at Aalto University. M. L. Oliveira, T. A. Bioni and H. Nawaz thanks FIPT, Capes, and FAPESP, respectively for their fellowships. O. A. El Seoud thanks CNPq for research productivity fellowships (grant 307022/2014-5 ) and FAPESP for financial support ( 2014/22136-4 ). H. Sixta and M. Hummel wish to thank Tekes – the Finnish Funding Agency for Innovation - and Finnish Bioeconomy Cluster FIBIC Ltd for funding. Publisher Copyright: © 2019

PY - 2019/5/15

Y1 - 2019/5/15

N2 - The efficiency of mixtures of ionic liquids (ILs) and molecular solvents in cellulose dissolution and derivatization depends on the structures of both components. We investigated the ILs 1-(1-butyl)-3-methylimidazolium acetate (C 4 MeImAc) and 1-(2-methoxyethyl)-3-methylimidazolium acetate (C 3 OMeImAc) and their solutions in dimethyl sulfoxide, DMSO, to assess the effect of presence of an ether linkage in the IL side-chain. Surprisingly, C 4 MeImAc-DMSO was more efficient than C 3 OMeImAc-DMSO for the dissolution and acylation of cellulose. We investigated both solvents using rheology, NMR spectroscopy, and solvatochromism. Mixtures of C 3 OMeImAc-DMSO are more viscous, less basic, and form weaker hydrogen bonds with cellobiose than C 4 MeImAc-DMSO. We attribute the lower efficiency of C 3 OMeImAc to “deactivation” of the ether oxygen and C2–H of the imidazolium ring due to intramolecular hydrogen bonding. Using the corresponding ILs with C2–CH 3 instead of C2–H, namely, 1-butyl-2,3-dimethylimidazolium acetate (C 4 Me 2 ImAc) and 1-(2-methoxyethyl)-2,3-dimethylimidazolium acetate (C 3 OMe 2 ImAc) increased the concentration of dissolved cellulose; without noticeable effect on biopolymer reactivity.

AB - The efficiency of mixtures of ionic liquids (ILs) and molecular solvents in cellulose dissolution and derivatization depends on the structures of both components. We investigated the ILs 1-(1-butyl)-3-methylimidazolium acetate (C 4 MeImAc) and 1-(2-methoxyethyl)-3-methylimidazolium acetate (C 3 OMeImAc) and their solutions in dimethyl sulfoxide, DMSO, to assess the effect of presence of an ether linkage in the IL side-chain. Surprisingly, C 4 MeImAc-DMSO was more efficient than C 3 OMeImAc-DMSO for the dissolution and acylation of cellulose. We investigated both solvents using rheology, NMR spectroscopy, and solvatochromism. Mixtures of C 3 OMeImAc-DMSO are more viscous, less basic, and form weaker hydrogen bonds with cellobiose than C 4 MeImAc-DMSO. We attribute the lower efficiency of C 3 OMeImAc to “deactivation” of the ether oxygen and C2–H of the imidazolium ring due to intramolecular hydrogen bonding. Using the corresponding ILs with C2–CH 3 instead of C2–H, namely, 1-butyl-2,3-dimethylimidazolium acetate (C 4 Me 2 ImAc) and 1-(2-methoxyethyl)-2,3-dimethylimidazolium acetate (C 3 OMe 2 ImAc) increased the concentration of dissolved cellulose; without noticeable effect on biopolymer reactivity.

KW - Biopolymer derivatization

KW - Cellulose dissolution

KW - Cellulose esters

KW - Ionic liquid-DMSO

KW - Solvatochromism

UR - https://www.scopus.com/pages/publications/85061769510

U2 - 10.1016/j.carbpol.2019.02.024

DO - 10.1016/j.carbpol.2019.02.024

M3 - Article

C2 - 30832848

AN - SCOPUS:85061769510

SN - 0144-8617

VL - 212

SP - 206

EP - 214

JO - Carbohydrate Polymers

JF - Carbohydrate Polymers

ER -

Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this