Molecular mechanism of cellulose dissolution in N-methyl morpholine-N-oxide: A molecular dynamics simulation study

N-methyl morpholine-N-oxide (NMMO) is the only commercialised solvent to dissolve cellulose and produce lyocell. However, the molecular mechanism of NMMO-induced cellulose solubilisation is unknown which limits further process development. In this work, and for the first time the complete dissolution process of a large cellulose bunch was simulated in NMMO monohydrate using long microsecond molecular dynamic simulations. The dissolution process was also simulated in 1-ethyl-3-methylimidazolium acetate (EmimAc) as an efficient ionic liquid in cellulose dissolution and the results were compared with the aqueous conditions. While the cellulose bunch showed a stable and insoluble structure in pure water, it was completely and efficiently dissolved in both NMMO monohydrate and EmimAc. It was shown that the dissolution time of cellulose in NMMO monohydrate is almost twice that in EmimAc, which is in agreement with the experimental observations. Although it is revealed that hydrogen bonding is the main driving force of cellulose dissolution in NMMO monohydrate, one cannot explain the complete molecular mechanism of NMMO-induced cellulose dissolution only by considering hydrogen bonds. A straightforward molecular mechanism was proposed, in which the interactions of NMMO molecules, not with cellulose, but with the other NMMO molecules play a critical role in the dissolution process.