Structuring of di-alkyl-urethanesils
- 85 Downloads
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.
KeywordsSol–gel chemistry Self-assembly Bridged silsesquioxane Structuring Di-alkyl-urethanesil
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.
Compliance with ethical standards
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.
All the co-authors have been informed of the content of the final version and I received their consent to submit it.
- 2.Graffion J, Cattoën X, Wong Chi Man M, Fernandes VR, André PS, Ferreira RAS, Carlos LD (2011) Modulating the photoluminescence of bridged silsesquioxanes incorporating Eu3+-complexed n,n′-diureido-2,2′-bipyridine isomers: application for luminescent solar concentrators. Chem Mater 23:4773–4782CrossRefGoogle Scholar
- 5.Arkles B (1999) Hybrid polymers in the marketplace - mix and match molecular building blocks to create better contact lenses, smoother-sailing ships, slippery surfaces, and move. Chemtech 29:7–14Google Scholar
- 10.Lindner E, Salesch T, Brugger S, Hoehn F, Wegner P, Mayer HA (2002) Supported organometallic complexes: Part XXX. Hydroformylation of 1-hexene in interphases—the influence of different kinds of inorganic–organic hybrid co-condensation agents on the catalytic activity. J Organomet Chem 641:165–172CrossRefGoogle Scholar
- 11.Creff G, Pichon BP, Blanc C, Maurin D, Sauvajol J-L, Carcel C, Moreau JJE, Roy P, Bartlett JR, Wong Chi Man M, Bantignies J-L (2013) Self-assembly of bridged silsesquioxanes: modulating structural evolution via cooperative covalent and noncovalent interactions. Langmuir 29:5581–5588CrossRefGoogle Scholar
- 12.Shea KJ, Moreau J, Loy DA, Corriu RJP, Boury B (2005) In: Gómez‐Romero P, Sanchez C (ed) Functional hybrid materials. Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimGoogle Scholar
- 13.Shea KJ, Loy DA (2001) Bridged Polysilsesquioxanes. Molecular-Engineered Hybrid Organic−Inorganic Materials, Chem Mater, 13, 3306–3319Google Scholar
- 32.Pereira RFP, Nunes SC, Toquer G, Cardoso MA, Valente AJM, Ferro MC, Silva MM, Carlos LD, Ferreira RAS, de Zea Bermudez V (2018) Novel highly luminescent amine-functionalized bridged silsesquioxanes. Front Chem 5:31Google Scholar
- 33.Nunes SC, de Zea Bermudez V (2018) Structuring of cross-linked non-bridged and bridged amide alkyl-based silsesquioxanes. Chem Rec Accepted for publication, 18, 1–14Google Scholar