Comparison of Cellulose Dissolution Behavior by Alkaline and Sulfuric Acid Solvents and Their Films’ Physical Properties

Three alkaline mixtures (NaOH/thiourea, NaOH/urea/thiourea, NaOH/urea/ZnO) and sulfuric acid were used at low temperatures as cellulose solvents, and their cellulose solubility and films’ physical properties for bleached chemical wood pulps and cotton linter were compared. Their degree of polymerization (DP) was controlled to 600–800 before dissolution. Among the alkaline solvents, NaOH/urea/ZnO gave the film the highest tensile strength and stretch. When compared to sulfuric acid, NaOH/urea/ZnO gave lower strength properties but higher crystallinity indices in the films. While alkaline solvents could not dissolve the high DP cellulose (DP ~ 2000), sulfuric acid could dissolve the high DP cellulose at below zero Celsius temperature, and the strength properties of the films were not much different from that of the low DP one. It appeared that the low-temperature sulfuric acid treatment did away with the cellulose’s DP controlling stage; it decreased cellulose DP very quickly for the high-DP cellulose at the initial stage, and as soon as the cellulose DP reached a DP low enough for dissolution, it began to dissolve the cellulose to result in stable cellulose solution.

Novel solvent systems for cellulose dissolution

Cellulose, as the most abundant sustainable resource on earth, can be chemically transformed into a variety of biodegradable materials, which have been proposed as the ideal substitutes for plastic products. The first challenge for the fabrication of cellulose-based functional materials is the successful dissolution of cellulose by solvents. However, most existing cellulose solvents have environmental, economic, and other drawbacks that limit their further industrial applications. Research on developing novel solvent systems with “greener” and “cheaper” properties is needed to meet the challenges.

Development of Diallylimidazolium Methoxyacetate/DMSO (DMF/DMA) Solvents for Improving Cellulose Dissolution and Fabricating Porous Material

Cellulose is the most abundant natural biopolymer, with unique properties such as biodegradability, biocompability, nontoxicity, and so on. However, its extensive application has actually been hindered, because of its insolubility in water and most solvents. Herein, highly efficient cellulose solvents were developed by coupling diallylimidazolium methoxyacetate ([A2im][CH3OCH2COO]) with polar aprotic solvents dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). Attractively, these solvents showed extraordinarily powerful dissolution performance for cellulose (e.g., 26.1 g·100g−1) in [A2im][CH3OCH2COO]/DMSO(RDMSO = 1.01 solvent even at 25 °C), which is much more advantageous over previously reported solvents. To our knowledge, such powerful cellulose solvents have not been reported before. The cellulose dissolution mechanism is proposed to be of three combined factors: (1) The hydrogen bond interactions of the H2, H4 and H6 in [A2im]+ and the carboxyl O atom in [CH3OCH2COO]−, along with the hydroxyl H atom and O atom in cellulose, are main driving force for cellulose dissolution; (2) the dissociation of [A2im][CH3OCH2COO] by DMF increases the anion and cation concentrations and thus promotes cellulose dissolution; (3) at the same time, DMF also stabilizes the dissolved cellulose chains. Meanwhile, the porous cellulose material with a varying morphologic structure could be facially fabricated by modulating the cellulose solution concentration. Additionally, the dissolution of cellulose in the solvents is only a physical process, and the regenerated cellulose from the solvents retains sufficient thermostability and a chemical structure similar to the original cellulose. Thus, this work will provide great possibility for developing cellulose-based products at ambient temperatures or under no extra heating/freezing conditions.

Dissolution performance of cellulose in [A2im][MOA]/MIM solvents

Cellulose solvents ([A2im][MOA]/MIM) were developed by combining diallylimidazolium methoxyacetate ([A2im][MOA]) with N-methylimidazole (MIM).

Dissolution Behavior of Cellulose in IL + DMSO Solvent: Effect of Alkyl Length in Imidazolium Cation on Cellulose Dissolution

Four cellulose solvents including [C2mim][CH3COO] + DMSO, [C4mim][CH3COO] + DMSO, [C6mim][CH3COO] + DMSO, and [C8mim][CH3COO] + DMSO were prepared by adding dimethyl sulfoxide DMSO in 1-ethyl-3-methylimidazolium acetate [C2mim][CH3COO], 1-butyl-3-methylimidazolium acetate [C4mim][CH3COO], 1-hexyl-3-methylimidazolium acetate [C6mim][CH3COO], and 1-octyl-3-methylimidazolium acetate [C8mim][CH3COO], respectively. The solubilities of cellulose in these solvents were determined at 25°C. The effect of the alkyl chain length in imidazolium cation on cellulose solubility was investigated. With increasing alkyl chain length in imidazolium cation, the solubility of cellulose increases, but further increase in alkyl chain length results in decreases in cellulose.