Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing

2018

Macromolecules

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Developing cellulose-based products is highly important because of their low-cost, reproducibility, and biodegradability. However, extensive application for cellulose has been actually hindered due to its well-known insolubility. Herein, some 22 novel functionalized imidazalium carboxylates exhibit tremendously enhanced dissolution capacity for cellulose even without extra energy consumption and are much superior to the previously reported solvents so far. Systematic investigations reveal that the powerful dissolution capacity for cellulose mainly results from the contribution of the imidazolium skeleton cation, not replacing acidic H atoms in imidazolium skeleton by alkyl, binding more allyl in N atoms of imidazolium cation, and binding an electron-donating group in carboxylate anion. Of particular importance, porous cellulose materials with varying micromorphology, for the first time, are reported by tuning the anionic and/or cationic structures of an IL. Moreover, the regenerated cellulose material retains sufficient thermostability and chemical structure. Therefore, this investigation provides a viable strategy for practical application in cellulose conversion into valuable products even without extra heating.

Section: Introductionmentioning

confidence: 99%

Functionalized Imidazalium Carboxylates for Enhancing Practical Applicability in Cellulose Processing

Chen

2018

Macromolecules

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“…Typical combinations include 1-butyl-3-methylimidazolium chloride + aprotic polar solvent (dimethyl sulfoxide (DMSO), N , N -dimethylformamide DMF, etc.) [34], 1-butyl-3-methylimidazolium acetate + DMSO (DMF or N , N -dimethylacetamide DMAc) [35,36,37,38] 1-allyl-3-methylimidazolium acetate + PEG [39], and piperazinium (piperidinium, pyrrolidinium) acetates + DMSO [39]. Compared with ILs, the IL + co-solvent systems have remarkable advantages, such as ease of dissolution for cellulose at low temperature, lowered viscosity, and cellulose dissolution efficiency.…”

Section: Introductionmentioning

confidence: 99%

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

Lin

et al. 2019

Polymers

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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.

“…Among them are 1-butyl-3-methylimidazolium chloride + cosolvent (dimethyl sulfoxide, N , N -dimethylformamide, etc.) 32 , 1-butyl-3-methylimidazolium acetate + cosolvent (dimethyl sulfoxide, N , N -dimethylformamide or N , N -dimethylacetamide) 33–36 , 1, 3-diallylimidazolium methoxyacetate + cosolvent (dimethyl sulfoxide, N,N -dimethylformamide or N,N -dimethylacetamide) 37 and 1-allyl-3-methylimidazolium acetate + PEG 38 . The solvent systems display lower dissolution temperature, higher cellulose solubility and lower viscosity than neat ILs.…”

Section: Introductionmentioning

confidence: 99%

Cellulose dissolution in diallylimidazolium methoxyacetate + N-methylpyrrolidinone mixture

Liu³

2019

Sci Rep

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The utilization of cellulose in industrial applicat is of great significance to sustainable development of human society and reducing dependence on dwindling fossil resources. Nevertheless, this utilization of cellulose has actually been limited due to its insolubilization. Here, novel solvents consisting of diallylimidazolium methoxy acetate ([A 2 im][CH 3 OCH 2 COO]) and N- methylpyrrolidinone (NMP) were developed. The solubility of cellulose in [A 2 im][CH 3 OCH 2 COO]/NMP was determined, and the influence of [A 2 im][CH 3 OCH 2 COO]/NMP molar ratio on cellulose dissolution was systematically investigated. Meanwhile, we also presented the affecting factors of the cellulose material fabrication including preparation approach, [A 2 im][CH 3 OCH 2 COO] and cellulose solution concentration. Attractively, the [A 2 im][CH 3 OCH 2 COO]/NMP solvents display much powerful dissolution capacity for cellulose even at 25 °C (25.4 g 100 g −1 ). This is mainly ascribed to the combined factors: The hydrogen bond interactions of the H2, H4 and H6 in [A 2 im] + and carboxyl O atom in [CH 3 OCH 2 COO] − with the hydroxyl H atom and O atom in cellulose; the dissociation of NMP towards [A 2 im][CH 3 OCH 2 COO]; the stabilization of NMP towards the dissolved cellulose chains. In addition, the thermostability and chemical structure of the regenerated cellulose from the solvents was also estimated.