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Synthesis of hydroxyurethanes-poly(dimethylsiloxane) with different chain terminations via carbon dioxide fixation: Characterizations and potential applications.

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Author(s):
Kelen Menezes Flores Rossi de Aguiar
Total Authors: 1
Document type: Doctoral Thesis
Press: São Carlos.
Institution: Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT)
Defense date:
Examining board members:
Ubirajara Pereira Rodrigues Filho; Hellmut Eckert; Debora Goncalves; Ana Maria de Guzzi Plepis; Klaus Rischka
Advisor: Ubirajara Pereira Rodrigues Filho
Abstract

Free isocyanate urethanes produced from an oligomeric precursor bis(cyclic carbonate) bearing poly(dimethylsiloxane) (CCPDMS) were synthesized in this work. Different primary amines such as 3-Aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) and monoamines 3-aminopropyltriethoxysilane (APTES), phenylethylamine (PEA), catechol amine (dopamine) and a decapeptide derived from marine mussel foot protein (mefp-1). The precursor cyclic carbonate CCPDMS was obtained from carbon dioxide fixation into epoxy rings catalized by a quaternary ammonium salt, tetraethylamonium bromide (TEAB). The precursor CCPDMS was reacted with the different amines by ring opening polymerization affording the formation of hydroxyurethanes PDMS derived (PDMSUr) with different chain terminations. Using APTES as chain terminator was feasible to obtain a hybrid material containing inorganic domains of organically modified silica (ormosil) interconnected to the organic part PDMS through urethane bond. In this hybrid matrix different mass percentages, varying from 1%wt to 55 wt%, of phosphotungstic acid (PWA) were added. The materials were characterized regarding their chemical structure by spectroscopic techniques (Nuclear Magnetic Resonance, Infrared, and X-ray photoelectron spectroscopy), mass spectrometry (MALDI-ToF and GPC), anti corrosive property (Electrochemical Impedance Spectroscopy and potentiodynamic polarization), surface properties (free surface energy, nanoindentation), morphology (Scanning Electron Microscopy), thermal stability (Thermogravimetric analysis), adhesion strenght measurements (pull-off-test and lap-shear), microbiologic assays (bacteria adhesion, tissue adhesion and citotoxicity test) besides photochromic assays. The polyoxometalate PWA provided photochromic property to the PDMSUr hybrid films presenting a maximum absorbance of 1.6 a.u after ultraviolet (UV) irradiation. Hybrids PDMSUr with or without PWA were tested as adhesive for glass, aluminium, steel (SS316L) and titanium alloy (Ti6Al4V) showing adhesion strength values ranging from 2-7 MPa. PDMSUr films prepared on different substrates showed bacteriostatic behavior against Escherichia coli (E.coli) and Lactobacillus casei (L.casei). The biomimetic PDMSUr catechol endcapped was able to form a layer on metallic surfaces showing good stability after rinsing with ethanol. (AU)

FAPESP's process: 11/06019-0 - CO2 uptake and synthesis of polyuretanes-polysilicone co-polymers as additives incorporated in ormosils: use on bioactive and ion conducting films
Grantee:Kelen Menezes Flores Rossi de Aguiar
Support Opportunities: Scholarships in Brazil - Doctorate