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Title: Intramolecular condensation reactions of {alpha},{omega}-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja961409k· OSTI ID:380900
; ; ;  [1]; ; ;  [2]
  1. Sandia National Lab., Albuquerque, NM (United States)
  2. Univ. of California, Irvine, CA (United States)

In this paper, we used mass spectrometry and {sup 29}Si NMR spectroscopy to discover that the length of the alkylene-bridging groups had a pronounced effect on the competition between cyclization and polymerization of {alpha},{omega}-bis(triethoxysilyl)alkanes and on the formation of polymeric gels. While the intramolecular reaction clearly slows gelation, the cyclic disilsesquioxanes are still tetrafunctional monomers theoretically capable of forming polymeric gels. If the ring structures, which bear a striking resemblence to carbohydrates, are preserved through the polymerization, the resulting poly(cyclic disilsesquioxane) gels may have structural similarities to branched or cross-linked carbohydrates, such as cellulose or chitosan. Under base-catalyzed sol-gel polymerization conditions, 3 and 4 (six- and seven-membered cyclic disilsesquioxanes, respectively) quickly reacted to give gels with significant ring opening as determined from the {sup 29}Si chemical shifts in solid-state (CP MAS) NMR spectra. However, gels prepared under acidic conditions reveal some or all of the cyclic disilsesquioxane functionality was preserved in the polymers. 13 refs., 1 fig.

Research Organization:
Sandia National Laboratories (SNL), Albuquerque, NM, and Livermore, CA (United States)
DOE Contract Number:
AC04-94AL85000
OSTI ID:
380900
Journal Information:
Journal of the American Chemical Society, Vol. 118, Issue 35; Other Information: PBD: 4 Sep 1996
Country of Publication:
United States
Language:
English