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纤维素在氢氧化钠/硫脲/尿素水溶液中的直接溶解

Direct dissolution of cellulose in NaOH/thiourea/urea aqueous solution.

作者信息

Jin Huajin, Zha Chunxi, Gu Lixia

机构信息

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 200051 Shanghai, China.

出版信息

Carbohydr Res. 2007 May 7;342(6):851-8. doi: 10.1016/j.carres.2006.12.023. Epub 2007 Jan 9.

Abstract

Untreated cellulose was directly and quickly dissolved in NaOH/thiourea/urea aqueous solution. The mechanism of dissolution was investigated by SEM, WXRD and (13)C NMR. The components of this solvent cannot dissolve cellulose on their own, and the interactions between NaOH and urea, as well as between NaOH and thiourea, play an important role in improving the dissolution of cellulose. Moreover, (13)C NMR spectra proved that NaOH, thiourea, and urea were bound to cellulose molecules, which brings cellulose molecules into aqueous solution to a certain extent and prevents cellulose macromolecules from associating. (13)C NMR spectra of the cellulose solution show that this novel mixture is a direct solvent. Optical microscopy and CP MAS (13)C NMR were used to study the process of dissolution. The results reveal that cellulose is dissolved completely and that cellulose I (cotton linter) first changes to amorphous cellulose chains in solution, and then to cellulose II during regeneration. Moreover, a new, more effective dissolution method is proposed, as confirmed by dynamic rheology measurements.

摘要

未处理的纤维素能直接且迅速地溶解于氢氧化钠/硫脲/尿素水溶液中。通过扫描电子显微镜(SEM)、广角X射线衍射(WXRD)和碳-13核磁共振(¹³C NMR)对溶解机理进行了研究。该溶剂的各组分自身无法溶解纤维素,氢氧化钠与尿素之间以及氢氧化钠与硫脲之间的相互作用在改善纤维素的溶解方面起着重要作用。此外,碳-13核磁共振谱证明氢氧化钠、硫脲和尿素与纤维素分子结合,这在一定程度上将纤维素分子带入水溶液中并防止纤维素大分子缔合。纤维素溶液的碳-13核磁共振谱表明这种新型混合物是一种直接溶剂。利用光学显微镜和交叉极化魔角旋转碳-13核磁共振(CP MAS ¹³C NMR)研究了溶解过程。结果表明纤维素完全溶解,纤维素I(棉短绒)在溶液中首先转变为无定形纤维素链,然后在再生过程中转变为纤维素II。此外,动态流变学测量证实了一种新的、更有效的溶解方法。

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