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

Chen, Huaxin; Yang, Fahui; Du, Jiehao; Xie, Haibo; Zhang, Lihua; Guo, Yuanlong; Xu, Qin; Zheng, Qiang; Li, Nanwen; Liu, Yu

doi:10.1007/s10570-018-2078-7

Cited by 30 publications

(22 citation statements)

References 31 publications

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“…In this system, cellulose is either derivatized reversibly with CO 2 in the presence of an organic superbase like 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to form a carbonate complex (derivative approach), which is then soluble in DMSO, or an alcohol like ethylene glycol or methanol is added, which forms the reversible carbonate complex and then acts as the solvent for cellulose dissolution (nonderivative approach). DBU was shown to fulfill a dual role in this system by being part of the solubilization process and acting as a derivatization catalyst in several cases. − …”

Section: Introductionmentioning

confidence: 99%

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

et al. 2021

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New sustainable concepts have to be developed to overcome the increasing problems of resource availability. Cellulose derivatives with tunable material properties are promising biobased alternatives to existing petroleum-derived polymeric materials. However, the chemical modification of cellulose is very challenging, often requiring harsh conditions and complex solubilization or activation steps. More sustainable procedures toward novel cellulose derivatives are therefore of great interest. Herein, we describe a novel concept combining two approaches, (i) tandem catalysis and (ii) cellulose derivatization, by applying a single catalyst for three transformations in the DMSO/DBU/CO2 switchable solvent system. Cellulose was functionalized with four different biobased isothiocyanates, which were formed in situ via a catalytic sulfurization of isocyanides with elemental sulfur, preventing the exposure and handling of the isothiocyanates. The degree of substitution of the formed O-cellulose thiocarbamates was shown to be controllable in a range of 0.52–2.16 by varying the equivalents of the reactants. All obtained products were analyzed by ATR-IR, 1H, 13C, and 31P NMR spectroscopy as well as size exclusion chromatography, elemental analysis, differential scanning calorimetry, and thermal gravimetric analysis. Finally, the tandem reaction approach was shown to be beneficial in terms of efficiency as well as sustainability compared to a stepwise synthesis. Recycling ratios ranging from 79.1% to 95.6% were obtained for the employed components, resulting in an E-factor of 2.95 for the overall process.

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Section: Introductionmentioning

confidence: 99%

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

et al. 2021

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“…Therefore, as a novel cellulose dissolution system with many merits, people have used the CO 2 switchable solvent for the synthesis of various cellulose derivatives, such as cellulose esters − and cellulose carbonates, and the preparation of regenerated cellulose materials, such as films, , hydrogel, and aerogel . These studies demonstrated its great feasibility for the dissolution, derivatization, and processing of cellulose .…”

Section: Introductionmentioning

confidence: 99%

Structure and Properties of Regenerated Cellulose Fibers Based on Dissolution of Cellulose in a CO₂ Switchable Solvent

Liu

et al. 2021

ACS Sustainable Chem. Eng.

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Development of an effective, nontoxic, and easy-to-process novel cellulose dissolution system for the preparation of regenerated cellulose fibers is of great importance and necessity for a greener and more sustainable future, with which the traditional viscose process with serious pollution can be gradually substituted. Herein, we demonstrated the successful utilization of a CO2 switchable solvent, a novel cellulose derivative dissolution system resembling viscose but without releasing toxic gases such as CS2 and H2S, for the preparation of regenerated cellulose fibers. The corncob cellulose raw material can be readily dissolved completely after the capture of CO2 in dimethyl sulfoxide (DMSO) with 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), resulting in cellulose spinning dope with high stability. Results showed that regenerated cellulose fibers with smoother surface morphology, a higher degree of crystallinity, and satisfactory mechanical properties were obtained under mild conditions with relatively slower double diffusion. Moreover, drawing treatment further increased the degree of crystallinity and orientation and the mechanical properties. All fibers had a dense structure, circular cross sections, no fibrillation, and high thermal stability. The regenerated cellulose fibers had degrees of crystallinity and orientation and tensile strength of 75.3%, 0.82, and 1.05 cN/dtex and 68.4%, 0.82, and 1.00 cN/dtex, respectively, in water and 30 vol % DMSO coagulation baths with a drawing ratio of 2.0 and 1.5, respectively. This work illustrated that the CO2 switchable solvent, which could be considered as “green viscose”, is a good candidate with great potential for the preparation of regenerated cellulose fibers with high performance and various functionalities in the future.

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“…Recently, a sustainable CO 2 -based solvent system for cellulose dissolution has been reported almost simultaneously by Xie et al [20] and by Zhang et al [21] Compared with the existing methods, this approach is a novel method in terms of its efficiency and sustainability. The potentials of this approach for developing cellulosic materials have been reported in synthesizing cellulose esters [22,23,24], cellulose grafted polylactic acid (PLA) [25], but regeneration of cellulose films under this system remains unreported.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Cellulose Films from Sustainable CO2/DBU/DMSO System

Jin

Gan

et al. 2019

Polymers

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Cellulose films are regarded as sustainable materials having wide applications in food packaging, separation, etc. Their preparation substantially relies on sufficient dissolution. Herein, various celluloses adequately dissolved in a new solvent system of carbon dioxide,1, 8-diazabicyclo [5.4.0] undec-7-ene and dimethyl sulfoxide (CO2/DBU/DMSO) were made in to films using different regeneration reagents. The films regenerated from ethanol and methanol presented homogeneous and smooth surfaces, while those from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) showed rough surfaces, as analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films regenerated from 5 wt % NaOH (aq.) and 5 wt % H2SO4 (aq.) rendered cellulose II structures, while those regenerated from alcohols had amorphous structures as evidenced using fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) results. The films made of microcrystalline cellulose had a good light transmittance of about 90% at 800 nm with a tensile strength of 55 MPa and an elongation break of 6.5%, while those from wood pulp cellulose demonstrated satisfactory flexibility with a tensile strength of 91 MPa and an elongation break of 9.0%. This research reports a simple, environmental, and sustainable method to prepare cellulose films of good mechanical properties.

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

Cited by 30 publications

References 31 publications

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

Structure and Properties of Regenerated Cellulose Fibers Based on Dissolution of Cellulose in a CO₂ Switchable Solvent

Preparation of Cellulose Films from Sustainable CO2/DBU/DMSO System

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

Cited by 30 publications

References 31 publications

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO2 Switchable Solvent System

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO2 Switchable Solvent System

Structure and Properties of Regenerated Cellulose Fibers Based on Dissolution of Cellulose in a CO2 Switchable Solvent

Preparation of Cellulose Films from Sustainable CO2/DBU/DMSO System

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Product

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Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO₂ Switchable Solvent System

Structure and Properties of Regenerated Cellulose Fibers Based on Dissolution of Cellulose in a CO₂ Switchable Solvent