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Volumn 119, Issue 13, 1997, Pages 3135-3143

n-Alkylsiloxanes: From single monolayers to layered crystals. The formation of crystalline polymers from the hydrolysis of n-octadecyltrichlorosilane

Author keywords

[No Author keywords available]

Indexed keywords

POLYMER; SILANE DERIVATIVE;

EID: 0030925720     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963284p     Document Type: Article
Times cited : (287)

References (82)
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    • Wen, J.1    Wilkes, G.L.2
  • 12
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    • and selected references therein
    • For a recent review, see: (a) Wen, J.; Wilkes, G. L. Chem. Mater. 1996, 8, 1667-1681 and references therein. See also: (b) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. Rev. 1995, 95, 1409-1430 and selected references therein. (c) Loy, D. A.; Shea, K. J. Ibid. 1995, 95, 1431-1442.
    • (1995) Chem. Rev. , vol.95 , pp. 1409-1430
    • Baney, R.H.1    Itoh, M.2    Sakakibara, A.3    Suzuki, T.4
  • 13
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    • For a recent review, see: (a) Wen, J.; Wilkes, G. L. Chem. Mater. 1996, 8, 1667-1681 and references therein. See also: (b) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. Rev. 1995, 95, 1409-1430 and selected references therein. (c) Loy, D. A.; Shea, K. J. Ibid. 1995, 95, 1431-1442.
    • (1995) Chem. Rev. , vol.95 , pp. 1431-1442
    • Loy, D.A.1    Shea, K.J.2
  • 20
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    • Willliams, P. A., Hudson, M. J., Eds.; Elsevier Applied Science: New York
    • (a) Alberti, G. In Recent Developments in Ion Exchange; Willliams, P. A., Hudson, M. J., Eds.; Elsevier Applied Science: New York, 1987.
    • (1987) Recent Developments in Ion Exchange
    • Alberti, G.1
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    • Cocke, D. L., Clearfield, A., Eds.; Plenum Press: New York
    • (b) Clearfield, A. In Design of New Materials; Cocke, D. L., Clearfield, A., Eds.; Plenum Press: New York, 1988.
    • (1988) Design of New Materials
    • Clearfield, A.1
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    • note
    • Since only small amounts of the acetone soluble fraction were available it was not characterized further. However, work is now in progress to characterize such soluble fractions as a function of chain lengths and preparation conditions.
  • 25
    • 1842397218 scopus 로고    scopus 로고
    • note
    • Details of the low-temperature thermal transistions of poly(n-alkylsiloxanes) will be reported elsewhere.
  • 60
    • 1842399170 scopus 로고    scopus 로고
    • note
    • Digitized optical function spectra are available upon request from D.L.A.
  • 61
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    • M.S. Thesis, The Pennsylvania State University
    • Shi, J. M.S. Thesis, The Pennsylvania State University, 1992.
    • (1992)
    • Shi, J.1
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    • note
    • 31P CPMAS NMR results on SAMs of octadecylsiloxane and zirconium octadecylphosphonate monolayers formed on nonporous, fumed silica and monodispersed silica colloids. They report an intense peak at 33 ppm, characteristic for a methylene carbon in an all-trans chain, and a much weaker peak at 30 ppm, characteristic for methylene carbons in disordered sequences. Their conclusion is that the ODS monolayers on the colloids are predominantly ordered, but less so than those typically reported on planar silica substrates, and are composed of coexisting domains of all-trans chains and of disordered chains.
  • 68
    • 1842348711 scopus 로고    scopus 로고
    • note
    • Preliminary attempts to grow larger single crystals by solution recrystallization as well as by control of pH and temperature during the synthesis stage were unsuccessful. Further work is in progress along these lines.
  • 70
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    • note
    • Consistent with this picture, from temperature-dependent IRS spectra we observe a disordering of the PODS alkyl chain structure at temperatures well below 160-170°C, accompanied by both a parallel diminution and rise of Si-OH and Si-O-Si stretching mode peak intensities, respectively. See ref 12.
  • 73
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    • note
    • x network, however, is complicated and is expected to be determined by a subtle interplay of the reactivities of the terminal silanols on the condensing siloxy chains as well as the local solution environment, especially pH. Under our conditions, HCl is released (reaction 1) creating an acidic pH. Alteration of this pH could be expected to introduce some changes in the siloxy microstrucrure, e.g., the acylic and cyclic segment composition, and the crystallite size. Studies are in progress in our laboratory to explore such effects.
  • 77
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    • Along these lines we note that a very recent in-situ atomic force microscopy study reports the observation of the coalesence of small domains into larger ones during alkylsiloxane monolayer growth. [Woodward, J. T.; Schwartz, D. K. J. Am. Chem. Soc. 1996, 118, 7861-7862].
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 7861-7862
    • Woodward, J.T.1    Schwartz, D.K.2
  • 78
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    • note
    • We also have sucessfully prepared other bilayered polyalkylsiloxane compound by hydrolysis of alkytrichlorosilanes for C12-C20 chains. All of these show conformational ordering by IRS but, as expected, the longer chains show higher ordering. These results will be reported elsewhere.


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