Skip to main content
SpringerLink
Log in

Efficient transesterification reaction of cellulose with vinyl esters in DBU/DMSO/CO2 solvent system at low temperature

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

Abstract

The transesterification reaction between cellulose and vinyl esters is regarded as a clean and facile strategy for the tunable synthesis of cellulose esters. In this study, a series of cellulose esters with degrees of substitution from 0.58 to 3.0 have been prepared successfully under mild conditions without adding any external catalysts when cellulose was dissolved in the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)/DMSO/CO2 solvent system and then followed by adding equimolar amounts of long chain fatty, aromatic, branched and steric vinyl esters. The optimization study of different reaction parameters like reaction time, temperature and amounts of substrates demonstrates that the reaction can proceed smoothly even at room temperature. This is evidenced by a cellulose benzoate with a DS of 2.6 obtained when the reaction is performed at 25 °C in 4 h. The as-prepared cellulose esters structure has been confirmed by 1H NMR, 13C NMR and FTIR, and material thermal properties were evaluated by DSC and TGA for an in-depth understanding the relationship between the cellulose esters structure and properties. It is believed that the DBU not only acts as a reagent for the CO2-derivative dissolution of cellulose in DMSO, but also acts as an in situ organocatalyst for the subsequent transesterification reaction.

Graphical abstract

Cellulose esters have been prepared successfully at low temperature using long chain fatty acids, aromatic, branched and steric vinyl esters as acyl donors in the DMSO/DBU/CO2 solvents system, and the DBU not only acts as reagents for the CO2-derivative dissolution of cellulose in DMSO, acts as an organocatalyst for the subsequent derivatisation.

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

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Barthel S, Heinze T (2006) Acylation and carbanilation of cellulose in ionic liquids. Green Chem 8:301–306

    Article  CAS  Google Scholar 

  • Cao Y, Zhang J, He J, Li H, Zhang Y (2010) Homogeneous acetylation of cellulose at relatively high concentrations in an ionic liquid. Chin J Chem Eng 18:515–522

    Article  CAS  Google Scholar 

  • Cao X, Sun S, Peng X, Zhong L, Sun R, Jiang D (2013) Rapid synthesis of cellulose esters by transesterification of cellulose with vinyl esters under the catalysis of NaOH or KOH in DMSO. J Agric Food Chem 61:2489–2495

    Article  CAS  Google Scholar 

  • Cao X, Peng X, Zhong L, Sun S, Yang D, Zhang X, Sun R (2014) A novel transesterification system to rapidly synthesize cellulose aliphatic esters. Cellulose 21:581–594

    Article  CAS  Google Scholar 

  • Çetin NS, Tingaut P, Özmen N, Henry N, Harper D, Dadmun M, Sèbe G (2009) Acetylation of cellulose nanowhiskers with vinyl acetate under moderate conditions. Macromol Biosci 9:997–1003

    Article  Google Scholar 

  • Chen M-J, Li R-M, Zhang X-Q, Feng J, Feng J, Liu C-F, Shi Q-S (2016) Homogeneous transesterification of sugarcane bagasse toward sustainable plastics. ACS Sustain Chem Eng 5:360–366

    Article  Google Scholar 

  • Cumpstey I (2013) Chemical modification of polysaccharides. ISRN Org Chem 2013:27

    Article  Google Scholar 

  • Dicke R (2004) A straight way to regioselectively functionalized polysaccharide esters. Cellulose 11:255–263

    Article  CAS  Google Scholar 

  • Freire CSR, Silvestre AJD, Neto CP, Belgacem MN, Gandini A (2006) Controlled heterogeneous modification of cellulose fibers with fatty acids: effect of reaction conditions on the extent of esterification and fiber properties. J Appl Polym Sci 100:1093–1102

    Article  CAS  Google Scholar 

  • Gao K, Chen Q, Hu Y, Zheng Q, Xie H (2016) Preparation and characterization of cellulose benzoate in CO2/DBU/DMSO. Sci Sin Chim 46:1337–1342

    Article  Google Scholar 

  • Gericke M, Fardim P, Heinze T (2012) Ionic liquids-promising but challenging solvents for homogeneous derivatization of cellulose. Molecules 17:7458–7502

    Article  Google Scholar 

  • Hanabusa H, Izgorodina EI, Suzuki S, Takeoka Y, Rikukawa M, Yoshizawa-Fujita M (2018) Cellulose-dissolving protic ionic liquids as low cost catalysts for direct transesterification reactions of cellulose. Green Chem 20:1412–1422

    Article  CAS  Google Scholar 

  • Heinze T, Dicke R, Koschella A, Kull AH, Klohr EA, Koch W (2000) Effective preparation of cellulose derivatives in a new simple cellulose solvent. Macromol Chem Phys 201:627–631

    Article  CAS  Google Scholar 

  • Hinner LP, Wissner JL, Beurer A, Nebel BA, Hauer B (2016) Homogeneous vinyl ester-based synthesis of different cellulose derivatives in 1-ethyl-3-methyl-imidazolium acetate. Green Chem 18:6099–6107

    Article  CAS  Google Scholar 

  • Itoh T, Nishimura Y, Ouchi N, Hayase S (2003) 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate: the most desirable ionic liquid solvent for recycling use of enzyme in lipase-catalyzed transesterification using vinyl acetate as acyl donor. J Mol Catal B Enzym 26:41–45

    Article  CAS  Google Scholar 

  • Junistia L, Sugih AK, Manurung R, Picchioni F, Janssen LPBM, Heeres HJ (2008) Synthesis of higher fatty acid starch esters using vinyl laurate and stearate as reactants. Starch-Stärke 60:667–675

    Article  CAS  Google Scholar 

  • Klemm D, Heublein B, Fink H-P, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Inter Ed 44:3358–3393

    Article  CAS  Google Scholar 

  • Mormann W, Al-Higari M (2004) Acylation of starch with vinyl acetate in water. Starch-Starke 56:118–121

    Article  CAS  Google Scholar 

  • Schenzel A, Hufendiek A, Barner-Kowollik C, Meier MAR (2014) Catalytic transesterification of cellulose in ionic liquids: sustainable access to cellulose esters. Green Chem 16:3266–3271

    Article  CAS  Google Scholar 

  • Shogren RL, Biswas A (2010) Acetylation of starch with vinyl acetate in imidazolium ionic liquids and characterization of acetate distribution. Carbohydr Polym 81:149–151

    Article  CAS  Google Scholar 

  • Song Y, Sun Y, Zhang X, Zhou J, Zhang L (2008) Homogeneous quaternization of cellulose in NaOH/urea aqueous solutions as gene carriers. Biomacromol 9:2259–2264

    Article  CAS  Google Scholar 

  • Song L, Yang Y, Xie H, Liu E (2015) Cellulose dissolution and in situ grafting in a reversible system using an organocatalyst and carbon dioxide. ChemSusChem 8:3217–3221

    Article  CAS  Google Scholar 

  • Tsuboi M (1957) Infrared spectrum and crystal structure of cellulose. J Polym Sci 25:159–171

    Article  CAS  Google Scholar 

  • Vicente G, Martinez M, Aracil J (2004) Integrated biodiesel production: a comparison of different homogeneous catalysts systems. Bioresour Technol 92:297–305

    Article  CAS  Google Scholar 

  • Xiao P, Zhang J, Feng Y, Wu J, He J, Zhang J (2014) Synthesis, characterization and properties of novel cellulose derivatives containing phosphorus: cellulose diphenyl phosphate and its mixed esters. Cellulose 21:2369–2378

    Article  CAS  Google Scholar 

  • Xie J, Hsieh YL (2001) Enzyme-catalyzed transesterification of vinyl esters on cellulose solids. J Polym Sci Part A Polym Chem 39:1931–1939

    Article  CAS  Google Scholar 

  • Xu Q, Song L, Zhang L, Hu G, Du J, Liu E, Zheng Q, Liu Y, Li N, Xie H (2017) Organocatalytic cellulose dissolution and in situ grafting of epsilon-caprolactone via ROP in a reversible DBU/DMSO/CO2 system. Chemistryselect 2:7128–7134

    Article  CAS  Google Scholar 

  • Xu Q, Song L, Zhang L, Hu G, Chen Q, Liu E, Liu Y, Zheng Q, Xie H, Li N (2018) Synthesis of cellulose acetate propionate and cellulose acetate butyrate in a CO2/DBU/DMSO system. Cellulose 25:205–216

    Article  CAS  Google Scholar 

  • Yang Y, Xie H, Liu E (2014) Acylation of cellulose in reversible ionic liquids. Green Chem 16:3018–3023

    Article  CAS  Google Scholar 

  • Yang Y, Song L, Peng C, Liu E, Xie H (2015) Activating cellulose via its reversible reaction with CO2 in the presence of 1,8-diazabicyclo 5.4.0 -undec-7-ene for the efficient synthesis of cellulose acetate. Green Chem 17:2758–2763

    Article  CAS  Google Scholar 

  • Zhang J, Wu J, Cao Y, Sang S, Zhang J, He J (2009) Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid. Cellulose 16:299–308

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant No. 31270637 and 21574030); Science and Technology Department of Guizhou Province (Grant No. Natural Science Key Fund [2016]1402), (Grant No. Platform & Talents [2016]5652); Open research fund of Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education of China (08031339); Foundation of State Key Laboratory of Coal Conversion (Grant No. J17-18-907); Excellent Scientific Innovative Talent Programme from Education Department of Guizhou Province (Grant No. KY[2015]479).

Author information

Authors and Affiliations

  1. Department of Polymer Materials and Engineering, College of Materials and Metullurgy, Guizhou University, Guiyang, 550025, China

    Huaxin Chen, Fahui Yang, Jiehao Du, Haibo Xie, Lihua Zhang, Yuanlong Guo, Qinqin Xu & Qiang Zheng

  2. Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education of China, Qilu University of Technology, Jinan, 250353, China

    Nanwen Li

  3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

    Yu Liu

Authors
  1. Huaxin Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Fahui Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiehao Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Haibo Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Lihua Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yuanlong Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qinqin Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Qiang Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Nanwen Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Yu Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Haibo Xie.

Ethics declarations

Conflicts of interest

There are no conflicts to declare.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1836 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, H., Yang, F., Du, J. et al. Efficient transesterification reaction of cellulose with vinyl esters in DBU/DMSO/CO2 solvent system at low temperature. Cellulose 25, 6935–6945 (2018). https://doi.org/10.1007/s10570-018-2078-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-018-2078-7

Keywords

Search

Navigation