Organic–inorganic tandem route to polymer nanocomposites: kinetic products versus thermodynamic products

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• 作者：Lingli Ni (1)
  Nadia Moreau (1)
  Abraham Chemtob (1)
  Céline Croutxé-Barghorn (1)
  
• 关键词：Hybrid ; Film ; Cationic polymerization ; RT ; FTIR ; Single ; step ; UV
• 刊名：Journal of Sol-Gel Science and Technology
• 出版年：2012
• 出版时间：November 2012
• 年：2012
• 卷：64
• 期：2
• 页码：500-509
• 全文大小：994KB
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• 作者单位：Lingli Ni (1)
  Nadia Moreau (1)
  Abraham Chemtob (1)
  Céline Croutxé-Barghorn (1)
  
  1. Laboratory of Photochemistry and Macromolecular Engineering, ENSCMu, University of Haute-Alsace, 3 rue Alfred Werner, 68093, Mulhouse Cedex, France
  
• ISSN：1573-4846

文摘

We report a facile single-step photochemical methodology to afford alkylsiloxane-polymer hybrid films which relies on the tandem photoacid-catalyzed polymerization of n-alkyltrimethoxysilane precursors and a diglycidyl ether organic monomer. Photoacids liberated by the UV decomposition of iodonium salt triggers simultaneously the sol–gel process and epoxy cationic polymerization. Such conditions are intended to favour the formation of kinetic products trapped by cross-linking reactions instead of the thermodynamically most stable structures, whose preference would be for macrophase segregation. Organosilane precursor exhibiting different structures and chain lengths (n-butyl, n-octyl, n-dodecyl, n-hexadecyl, isobutyl and isooctyl) were systematically investigated to afford a range of transparent alkylsiloxane-polyether hybrids. The competitive organic–inorganic reaction kinetics were investigated using in situ real-time Fourier transform infrared spectroscopy. A main emphasis has been on discussing the effect of the alkyl substituent structure on the photoinduced polymerization kinetics and the silicate networks characterized by 29Si solid-state NMR. To avoid phase separation, the rate of formation of the two phases was tailored to favour concomitancy upon modulating several experimental parameters: film thickness, alkyl structure, photoacid generator concentration. Finally, the viscoelastic and surface properties were also assessed by dynamic mechanical analysis and water contact angle measurements, respectively.