1 College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science & Technology, Xi’an 710021; 2 Key Laboratory of Leather Cleaner Production, China National Light Industry,Xi’an 710021
Abstract: Cellulose, as one of the most abundant natural polymer and the most promising green materials with renewability, biocompatibility and biodegradability, etc., has become a hot spot for its effective utilization in the fields of chemistry, chemical engineering and materials science. The recent research of cellulose is mainly concentrated in the following three aspects: Ⅰ. the direct processing of the cellulose solution formed from environment-friendly solvent systems; Ⅱ. the preparation of cellulose derivative or graft copolymer which can be dissolved in common solvent by attenuating the intra- and inter-molecular hydrogen bonding interactions of cellulose via chemical modification; Ⅲ. the construction of novel cellulose functional materials by introducing specific chemical groups or other polymers into the cellulose derivatives structural units. On the other hand, the cellulose chemical modification reactions are conventionally carried out in multiphase medium, due to the lack of effective solvent for cellulose, resulting in complex process, poor product homogeneity, difficulty in structure control and high energy consumption, etc. Thus the development of new solvent systems for cellulose chemical reaction has been regarded as a plausible countermeasure. In the past few decades, there have emerged a variety of solvent systems which are more effective in dissolving cellulose, including N,N-dimethylacetamide/lithium chloride (DMAc/LiCl), polyoxymethylene/dimethyl sulfoxide (PF/DMSO), DMSO/tetrabutylammonium fluoride trihydrate (DMSO/TBAF·3H2O), N-methylmorpholine oxide (NMMO), ionic liquids (ILs), some molten salt hydrates, alkali/urea aqueous systems, etc. Among them, DMAc/LiCl and ILs have displayed the potential as the ideal solvents for homogeneous esterification and graft copolymerization of cellulose, mainly for their high chemical stability. Alkali/urea aqueous systems are considered to be excellent medium for homogeneous etherification of cellulose due to the existence of alkali. The homogeneous chemical modification of cellulose opens a new way for the development of simple, economical, efficient and highly qualitative cellulose-based functional materials. By adopting the above mentioned systems, an extensive range of cellulose-based materials (e.g., regenerated cellulose fibers, films, hydrogels, aerogels, composites, and cellulose esters, ethers, graft copolymers) have been fabricated successfully from cellulose as raw material. The TEMPO-mediated oxidation, aldehyde-amino Schiff reaction, covalent crosslinking, azide-alkyne cycloaddition, thiol-ene "click chemistry" reaction, living/controlled free radical polymerization such as atom transfer radical polymerization (ATRP), nitroxide-mediated living free-radical polymerizations (NMP) and reversible addition fragmentation chain transfer polymeri-zation (RAFT), have assumed future-representativeness in the preparation of cellulose based polymers. These revamped methods establish a new and versatile platform for cellulose processing and functionalization, providing satisfactory and widely applicable cellulose-based products for drug delivery and controlled release, sewage purification, papermaking, coating fabrication. In addition, cellulose derivatives can also be used as structural units to construct cellulose materials with novel structure or functions. The formed graft polymers are able to demonstrate self-assembly behavior under certain circumstances. This review makes a retrospection of the research efforts with respect to oxycellulose, and the homogeneous derivatization and graft copolymerization of cellulose through which can novel functionallized cellulose materials be obtained, then sketches out the advances in creating cellulose hydrogels by crosslinking of cellulose. We comparatively analyse the principles and characteristics of synthesizing cellulose graft copolymers by traditional free radical polymerization, ionic polymerization, ring-opening polymerization (ROP) and living/controlled free radical polymerization, and finally outline the future development trend.
姚一军,王鸿儒. 纤维素化学改性的研究进展[J]. 材料导报, 2018, 32(19): 3478-3488.
YAO Yijun, WANG Hongru. An Overview on Chemical Modification of Cellulose. Materials Reports, 2018, 32(19): 3478-3488.
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2018, Vol. 32 
