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 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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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.
Conflict of interest
The authors declare that they have no conflicts of interest.
I hereby declare that the present manuscript is completely original and has not been submitted to more than one journal for simultaneous consideration. The manuscript has not been published previously (partly or in full). No reported data have been fabricated or manipulated (including images) to support our conclusions. This research did not involve Human Participants and/or Animals.
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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
- Sol–gel chemistry
- Bridged silsesquioxane