Cellulose Ester Films Preparation in a DBU–CO2 Switchable Solvent: From Batch Synthesis to Reactive Extrusion at High-Solid Content
Abstract
The direct transesterification of cellulose with vinyl laurate (VL) was investigated in the DMSO–DBU–CO2 switchable solvent system and subsequently translated to reactive extrusion (R-EX) under high-solid conditions, offering a simple and catalyst-free route for the preparation of long-chain cellulose esters. In a homogeneous medium, degree of substitution (DS) was tuned by varying the anhydroglucose unit (AGU):VL molar ratio (1:1–1:5). FTIR and NMR confirmed progressive hydroxyl substitution, with DS increasing with VL feed. The resulting cellulose laurates showed enhanced thermal stability and hydrophobicity, while higher DS reduced stiffness and increased flexibility due to internal plasticization by lauryl side chains. To overcome the inherent limitations of batch processes─namely, low cellulose concentration and long reaction times─the system was successfully extended to R-EX up to 22 wt % cellulose. Under these conditions, transesterification proceeded rapidly at moderate temperatures, yielding transparent, ductile, and hydrophobic films with DS comparable to those obtained in solution. A DOZN green-chemistry assessment of the esterification step showed that R-EX reduced the DOZN score by nearly 60% compared with the batch protocol. This study demonstrates that the DMSO–DBU–CO2 medium constitutes a solvent-lean platform for the sustainable preparation of cellulose esters. Its integration with R-EX provides a process-intensified route toward high-performance, biobased materials with tunable mechanical and surface properties.
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BibTeX
@article{aouay2026cellulose,
title = {{Cellulose Ester Films Preparation in a DBU–CO2 Switchable Solvent: From Batch Synthesis to Reactive Extrusion at High-Solid Content}},
author = {Mohamed Aouay and Thomas Vidil and Adèle Gapin and Eric Cloutet and Sylvain Chambon and Stéphane Grelier and Henri Cramail},
journal = {ACS Applied Polymer Materials},
year = {2026},
month = aug,
doi = {10.1021/acsapm.6c02064},
url = {https://hal.science/hal-05739288v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Cellulose Ester Films Preparation in a DBU–CO2 Switchable Solvent: From Batch Synthesis to Reactive Extrusion at High-Solid Content
AU - Mohamed Aouay
AU - Thomas Vidil
AU - Adèle Gapin
AU - Eric Cloutet
AU - Sylvain Chambon
AU - Stéphane Grelier
AU - Henri Cramail
PY - 2026
DA - 2026/08/29
JO - ACS Applied Polymer Materials
DO - 10.1021/acsapm.6c02064
UR - https://hal.science/hal-05739288v1
AB - The direct transesterification of cellulose with vinyl laurate (VL) was investigated in the DMSO–DBU–CO2 switchable solvent system and subsequently translated to reactive extrusion (R-EX) under high-solid conditions, offering a simple and catalyst-free route for the preparation of long-chain cellulose esters. In a homogeneous medium, degree of substitution (DS) was tuned by varying the anhydroglucose unit (AGU):VL molar ratio (1:1–1:5). FTIR and NMR confirmed progressive hydroxyl substitution, with DS increasing with VL feed. The resulting cellulose laurates showed enhanced thermal stability and hydrophobicity, while higher DS reduced stiffness and increased flexibility due to internal plasticization by lauryl side chains. To overcome the inherent limitations of batch processes─namely, low cellulose concentration and long reaction times─the system was successfully extended to R-EX up to 22 wt % cellulose. Under these conditions, transesterification proceeded rapidly at moderate temperatures, yielding transparent, ductile, and hydrophobic films with DS comparable to those obtained in solution. A DOZN green-chemistry assessment of the esterification step showed that R-EX reduced the DOZN score by nearly 60% compared with the batch protocol. This study demonstrates that the DMSO–DBU–CO2 medium constitutes a solvent-lean platform for the sustainable preparation of cellulose esters. Its integration with R-EX provides a process-intensified route toward high-performance, biobased materials with tunable mechanical and surface properties.
SN - 2637-6105
ER -