Organotrialkoxysilanes containing secondary hydroxyl groups were synthesized by reacting 1 mole of (3-aminopropyl)triethoxysilane (APS) with 1 or 2 mole of phenylglycidylether (PGE). Resulting products, APS-PGE and APS-PGE2, respectively, were subjected to hydrolytic condensation at 50 °C during 24 h. For APS-PGE, the reaction was performed using a molar ratio [H2O]/Si=3, without addition of an external catalyst. For APS-PGE2, the reaction was catalyzed by HCOOH or NaOH. Resulting poly(silsesquioxanes) (PSSO) were characterized by size exclusion chromatography, Fourier-transformed infrared spectroscopy and matrix-assisted ultraviolet laser desorption/ionization time-of-flight mass spectrometry (UV-MALDI-TOF MS). PSSO derived from APS-PGE and APS-PGE2, catalyzed by HCOOH, exhibited a relatively narrow distribution of polyhedral structures. This constitutes a simple one-step synthesis of polyhedral oligomeric silsesquioxanes (POSS) functionalized with amine and/or hydroxyl groups. The directionality of the reaction pathway towards the formation of polyhedral structures was ascribed to the formation of intramolecular Si-O-C bonds through the reaction of SiOEt or SiOH groups with secondary hydroxyl groups. Intramolecular Si-O-C bonds were found in the structures of APS-PGE and APS-PGE2, and in most of the species of the PSSO obtained from the NaOH-catalyzed reaction of APS-PGE2. A small fraction of surviving Si-O-C bonds was also found in the polyhedral structures of the PSSO derived from the hydrolytic condensation of APS-PGE and APS-PGE2 catalyzed by formic acid. By usual organic reactions transforming hydroxyl groups into other functional groups, it is possible to generate narrow distribution of multi-functionalized POSS starting from an OH-functionalized organotrialkoxysilane. © 2003 Elsevier Science B.V. All rights reserved.
Documento: | Artículo |
Título: | Poly(silsesquioxanes) derived from the hydrolytic condensation of organotrialkoxysilanes containing hydroxyl groups |
Autor: | dell'Erba, I.E.; Fasce, D.P.; Williams, R.J.J.; Erra-Balsells, R.; Fukuyama, Y.; Nonami, H. |
Filiación: | Inst. of Mat. Science/Technology, University of Mar del Plata, CONICET, J.B. Justo 4302, 7600 Mar del Plata, Argentina CIHIDECAR-CONICET, Department of Organic Chemistry, University of Buenos Aires, Pab. 2, 1428 Buenos Aires, Argentina Biochemistry Research Laboratory, College of Agriculture, Ehime University, Matsuyama 790-8566, Japan |
Palabras clave: | OH-functionalized organotrialkoxysilanes; Poly(silsesquioxanes); Polyhedral oligomeric silsesquioxanes (POSS); S O C bonds; UV-MALDI-TOF MS; 3 aminopropyltriethoxysilane; amide; carbon; ether derivative; formic acid; hydroxyl group; oxygen; silane derivative; silicon; sodium hydroxide; water; article; catalyst; chemical bond; chemical reaction; chemical structure; controlled study; gel permeation chromatography; hydrolysis; infrared spectroscopy; matrix assisted laser desorption ionization time of flight mass spectrometry; polymerization; synthesis; temperature; time |
Año: | 2003 |
Volumen: | 686 |
Número: | 1-2 |
Página de inicio: | 42 |
Página de fin: | 51 |
DOI: | http://dx.doi.org/10.1016/S0022-328X(03)00377-2 |
Título revista: | Journal of Organometallic Chemistry |
Título revista abreviado: | J. Organomet. Chem. |
ISSN: | 0022328X |
CODEN: | JORCA |
CAS: | 3 aminopropyltriethoxysilane, 919-30-2; amide, 17655-31-1; carbon, 7440-44-0; formic acid, 64-18-6, 71-47-6; oxygen, 7782-44-7; silicon, 7440-21-3; sodium hydroxide, 1310-73-2; water, 7732-18-5 |
Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0022328X_v686_n1-2_p42_dellErba |