Silylation of Cellulose with Hexamethyldisilazane in Ammonia – Activation, Catalysis, Mechanism, Properties

作者: Werner Mormann

DOI: 10.1023/A:1025100829371

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摘要: Synthesis of trimethylsilylcellulose (TMSC) from cellulose and hexamethyldisilazane (HMDS) in liquid ammonia is reviewed, with emphasis on the scope reaction mechanistic features. Conditions for complete controlled stoichiometric partial silylation have been established. Stoichiometric desilylation TMSC also possible tetrahydrofuran containing as hydrogen bond donor. The activating effect ammonia, solubility reactants, catalysis kinetics heterogeneous are discussed. Silylation follows first order presence saccharin catalyst, indicating that accessibility hydroxy groups not rate-determining factor. TMSCs a window THF DS 1.6 to 2.6. This narrower higher molecular weight TMSC.

参考文章(25)
Kurt Hess, Josef Gundermann, Über die Einwirkung von flüssigem Ammoniak auf Cellulosefasern (Bildung von Ammoniak-Cellulose I, Ammoniak-Gellulose II und Cellulose III) Berichte der deutschen chemischen Gesellschaft (A and B Series). ,vol. 70, pp. 1788- 1799 ,(1937) , 10.1002/CBER.19370700825
Harry Schleicher, Carola Daniels, Burkart Philipp, Changes of cellulose accessibility to reactions in alkaline medium by activation with ammonia Journal of Polymer Science: Polymer Symposia. ,vol. 47, pp. 251- 260 ,(1974) , 10.1002/POLC.5070470130
J. A. McHard, P. C. Servais, H. A. Clark, Determination of Silicon in Organosilicon Compounds Analytical Chemistry. ,vol. 20, pp. 325- 328 ,(1948) , 10.1021/AC60016A015
R. E. Harmon, K. K. De, S. K. Gupta, Preparation of Trimethylsilyl Derivatives of Polysaccharides Starch - Stärke. ,vol. 25, pp. 429- 431 ,(1973) , 10.1002/STAR.19730251211
E. Husemann, O. H. Weber, Die Bestimmung des Molekulargewichtes von Cellulosen nach einer Endgruppenmethode. 304. Mitteilung über makromolekulare Verbindungen Journal Fur Praktische Chemie-chemiker-zeitung. ,vol. 161, pp. 1- 19 ,(1942) , 10.1002/PRAC.19421610101
W. T. Grubb, A Rate Study of the Silanol Condensation Reaction at 25° in Alcoholic Solvents1 Journal of the American Chemical Society. ,vol. 76, pp. 3408- 3414 ,(1954) , 10.1021/JA01642A014
M. A. Rousselle, M. L. Nelson, C. B. Hassenboehler, D. C. Legendre, Liquid-Ammonia and Caustic Mercerization of Cotton Fibers: Changes in Fine Structure and Mechanical Properties: Textile Research Journal. ,vol. 46, pp. 304- 310 ,(1976) , 10.1177/004051757604600412
W. Schempp, U. Seifried, A. Koura, T. Krause, Herstellung hochsubstituierter Trimethylsilylcellulosen im System Dimethylacetamid/Lithium chlorid Das Papier. ,vol. 38, pp. 607- 610 ,(1984)