Nanocellulose has been subjected to a wide range of chemical modifications towards increasing its potential in certain fields of interest. These modifications either modulated the chemistry of the nanocellulose itself or introduced certain functional groups onto its surface, which varied from simple molecules to polymers. Among many, aliphatic and aromatic mono- and di-isocyanates are a group of chemicals that have been used for a century to modify cellulose. Despite only being used recently with nanocellulose, they have shown great potential as surface modifiers and chemical linkers to graft certain functional chemicals and polymers onto the nanocellulose surface. This review discusses the modification of cellulose and nanocellulose using isocyanates including phenyl isocyanate (PI), octadecyl isocyanate (OI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), and their derivatives and polymers. It also presents the most commonly used nanocellulose modification strategies including their advantages and disadvantages. It finally discusses the challenges of using isocyanates, in general, for nanocellulose modification.
Ionic liquids have shown great potential in the last two decades as solvents, catalysts, reaction media, additives, lubricants, and in many applications such as electrochemical systems, hydrometallurgy, chromatography, CO2 capture, etc. As solvents, the unlimited combinations of cations and anions have given ionic liquids a remarkably wide range of solvation power covering a variety of organic and inorganic materials. Ionic liquids are also considered “green” solvents due to their negligible vapor pressure, which means no emission of volatile organic compounds. Due to these interesting properties, ionic liquids have been explored as promising solvents for the dissolution and fractionation of wood and cellulose for biofuel production, pulping, extraction of nanocellulose, and for processing all-wood and all-cellulose composites. This review describes, at first, the potential of ionic liquids and the impact of the cation/anion combination on their physiochemical properties and on their solvation power and selectivity to wood polymers. It also elaborates on how the dissolution conditions influence these parameters. It then discusses the different approaches, which are followed for the homogeneous and heterogeneous dissolution and fractionation of wood and cellulose using ionic liquids and categorize them based on the target application. It finally highlights the challenges of using ionic liquids for wood and cellulose dissolution and processing, including side reactions, viscosity, recyclability, and price.
Abstract:Imidazole is reported to be an effective reactant for the production of nanocellulose from hardwood pulp. The morphologies and surface properties of the nanocellulose can be simply tailored according to the water content in the imidazole system: with pure imidazole, cellulose nanofibrils (CNFs) in a yield of 10 wt % can be produced. With 25 wt % of water in imidazole, cellulose nanocrystals (CNCs) are obtained in 20 wt % yield. Both nanocelluloses exhibit crystallinity indices in the order of 70%. Interestingly, they retain the original xylan from the pulp with ca. 9-10 wt % of residual xylan content.
The hydrophilicity of cellulose nanocrystals (CNCs) is a major challenge for their processing with hydrophobic polymers and matrices. As a result, many surface modifications have been proposed to hydrophobize CNCs. The authors showed in an earlier study that grafting alcohols of different chain lengths onto the surface of CNCs using toluene diisocyanate (TDI) as a linker can systematically hydrophobize CNCs to a water contact angle of up to 120° depending on the alcohol chain length. Then, the hydrophobized CNCs were used to mechanically reinforce poly(butylene succinate) (PBS), which is a hydrophobic polymer. As a result of hydrophobization, PBS/CNCs interfacial adhesion and the composite mechanical properties significantly improved with the increasing CNC contact angle. Continuing on these results, this paper investigates the impact of CNC surface properties on the crystallization behavior of PBS using differential scanning calorimetry (DSC). The results showed that the crystallization temperature of PBS increased from 74.7 °C to up to 86.6 °C as a result of CNC nucleation activity, and its value was proportionally dependent on the contact angle of the CNCs. In agreement, the nucleation activity factor (φ) estimated using Dobreva and Gutzow’s method decreased with the increasing CNC contact angle. Despite the nucleation action of CNCs, the rate constant of PBS crystallization as estimated using the Avrami model decreased in general as a result of a prevailing impeding effect. This decrease was minimized with increasing the contact angle of the CNCs. The impeding effect also increased the average activation energy of crystallization, which was estimated using the Kissinger method. Moreover, the Avrami exponent (n) decreased because of CNC addition, implying a heterogeneous crystallization, which was also apparent in the crystallization thermograms. Overall, the CNC addition facilitated PBS nucleation but retarded its crystallization, and both processes were significantly affected by the surface properties of the CNCs.
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