Volume 34, Issue 2 pp. 277-289
Article

Synthesis, isomerization, and polymerization of mixed phosphoranimines

Michael L. White

Michael L. White

Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave., Pittsburgh, Pennsylvania 15213

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Krzysztof Matyjaszewski

Corresponding Author

Krzysztof Matyjaszewski

Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave., Pittsburgh, Pennsylvania 15213

Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave., Pittsburgh, Pennsylvania 15213Search for more papers by this author

Abstract

A series of phosphites were prepared bearing various combinations of phenoxy, methoxy, and trifluoroethoxy substituents. (PhO)3P, (CF3CH2O)(PhO)2P, (CF3CH2O)2(PhO)P, and (CH3OCH2CH2O)(PhO)2P were polymerized during the course of the Staudinger reaction with azidotrimethylsilane to form low molecular weight polyphosphazenes. Similar reactions with (CH3O)(CF3CH2O)2P, (CH3O)(PhO)2P, (CH3O)2(CF3CH2O)P, (CH3O)2(PhO)P, and (CH3O)3P produced the desired phosphoranimine as well as the corresponding phosphoramidate isomer. Studies were performed on these systems in order to understand the nature of this isomerization. (CH3O)(PhO)2P (DOUBLE BOND) N (SINGLE BOND) Si(CH3)3 and (CH3O)2(PhO)P (DOUBLE BOND) N (SINGLE BOND) Si(CH3)3 polymerize at temperatures above 150°C. © 1996 John Wiley & Sons, Inc.

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