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Structuring of di-alkyl-urethanesils

Abstract

A novel organized di-urethane crossed-linked dodecyl/siloxane (di-alkyl-urethanesil) was synthesized by the sol–gel process and self-directed assembly, from the organosilane precursor (CH3CH2O)3-Si-(CH2)3-NHC( = O)O-(CH2)12-O(O = C)NH-(CH2)3-Si-(OCH2CH3)3, through a fine control of the reaction conditions (hyper-stoichiometric amount of water, minor amount of tetrahydrofuran, and acid catalysis; molar ratio Si:H2O:HCl:THF = 1:300:0.1:12.5). The new bridged silsesquioxane was identified by the notation d-Ut(CY)AC, where Y = 12 is the number of carbon atoms C of the bridging alkyl chains and AC represents acid catalysis. The d-Ut(C12)AC material exhibits a structured lamellar organization with medium long-range order, a texture composed of homogeneous lamellae immersed in a sponge-like matrix made of randomly distributed thin plates, and is thermally stable up to ca. 350 °C. Despite the hydrophobic nature of the dodecane chains, the weakness of the urethane–urethane hydrogen-bonded array formed led to the growth of moderately ordered assemblies of amphiphilic organo(bis-silanetriol) substructures comprising mainly all-trans conformers.

A lamellar di-urethane cross-linked dodecyl/siloxane (di-alkyl-urethanesil) with medium long-range order, a texture composed of homogeneous lamellae immersed in a sponge-like matrix made of randomly distributed thin plates, and an average water contact angle of 94.17 ± 17.10°, was synthesized by the sol–gel process and self-directed assembly.

Highlights

  • A di-urethane crossed-linked dodecyl/siloxane was produced using a controlled hydrolytic sol–gel route.

  • The material exhibits a structured lamellar organization with medium long-range order.

  • The morphology of the material includes homogeneous lamellae immersed in a sponge-like matrix.

  • The material is thermally stable up to ca. 350 °C.

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Acknowledgements

This work was supported by FEDER, through COMPETE and Fundação para a Ciência e a Tecnologia (FCT) (Pest-OE/QUI/UI0616/2014 and PEst-OE/SAU/UI0709/2014) and LUMECD project (POCI-01-0145-FEDER-016884 and PTDC/CTM-NAN/0956/2014), project UniRCell (Ref. SAICTPAC/0032/2015, POCI-01-0145-FEDER-016422). S.C. Nunes and R.F.P. Pereira acknowledge Post-PhD Fellowships of LUMECD project and SFRH/BPD/87759/2012 grant, respectively.

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Gonçalves, M.C., Pereira, R.F.P., Ferreira, P. et al. Structuring of di-alkyl-urethanesils. J Sol-Gel Sci Technol 89, 205–215 (2019). https://doi.org/10.1007/s10971-018-4703-1

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Keywords

  • Sol–gel chemistry
  • Self-assembly
  • Bridged silsesquioxane
  • Structuring
  • Di-alkyl-urethanesil