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真分子溶液天然纤维素在二元离子液体溶剂混合物中。

True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures.

机构信息

Faculty of Chemical Engineering, Technion - Israel Institute of Technology, Haifa 32000, Israel.

Jülich Centre for Neutron Science, Forschungszentrum Jülich GmbH Outstation at MLZ, 85747 Garching, Germany.

出版信息

Carbohydr Polym. 2014 Nov 4;112:125-33. doi: 10.1016/j.carbpol.2014.05.059. Epub 2014 Jun 2.

Abstract

Evidence is presented for the first time of true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with ionic liquid. Cryogenic transmission electron microscopy, small-angle neutron-, X-ray- and static light scattering were used to investigate the structure of cellulose solutions in mixture of dimethyl formamide and 1-ethyl-3-methylimidazolium acetate. Structural information on the dissolved chains (average molecular weight ∼ 5 × 10(4)g/mol; gyration radius ∼ 36 nm, persistence length ∼ 4.5 nm), indicate the absence of significant aggregation of the dissolved chains and the calculated value of the second virial coefficient ∼ 2.45 × 10(-2)mol ml/g(2) indicates that this solvent system is a good solvent for cellulose. More facile dissolution of cellulose could be achieved in solvent mixtures that exhibit the highest electrical conductivity. Highly concentrated cellulose solution in pure ionic liquid (27 wt.%) prepared according to novel method, utilizing the rapid evaporation of a volatile co-solvent in binary solvent mixtures at superheated conditions, shows insignificant cellulose molecular aggregation.

摘要

首次提出了纤维素在常见极性有机溶剂与离子液体的二元混合物中真正分子溶解的证据。使用低温透射电子显微镜、小角中子、X 射线和静态光散射研究了纤维素在二甲基甲酰胺和 1-乙基-3-甲基咪唑乙酸盐混合物中的溶液结构。关于溶解链的结构信息(平均分子量约为 5×10(4)g/mol;回转半径约为 36nm,持久长度约为 4.5nm)表明溶解链没有明显的聚集,计算得到的第二维里系数约为 2.45×10(-2)mol ml/g(2),表明该溶剂体系是纤维素的良溶剂。在电导率最高的溶剂混合物中,可以更轻易地溶解纤维素。根据新方法,在过热条件下利用二元溶剂混合物中挥发性共溶剂的快速蒸发,在纯离子液体(27wt%)中制备出高浓度纤维素溶液,纤维素分子没有明显聚集。

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