Collect. Czech. Chem. Commun. 1997, 62, 442-456

Study of Polycondensation of Tetraethoxysilane Catalyzed with Dibutylbis[1-oxo(dodecyl)oxy]stannane Using 1H NMR and 29Si NMR Spectrometry and Quasi Elastic Light Scattering

Jiří Brusa, Petr Kotlíka and Jiří Karhanb

a Department of Chemical Technology of Monuments Conservation, Prague Institute of Chemical Technology, 166 28 Prague 6, Czech Republic
b Central NMR Laboratory, Prague Institute of Chemical Technology, 166 28 Prague 6, Czech Republic


The polycondensation of tetraethoxysilane (TEOS) catalyzed with dibutylbis[1-oxo(dodecyl)oxy]stannane (dibutyltin dilaurate, DBTDL) has been investigated with the help of 1H and 29Si NMR spectrometry and quasi elastic light scattering (QELS). It has been found that in contrast to the acid catalyzed polycondensation the siloxane chain grows in linear and branched way, the proportion of cyclization reactions being slight. The rate of chain growth is relatively high, which is indicated by the impossibility to detect the presence of shorter oligomers in the reaction mixture by means of 29Si NMR. The found rate constant of polycondensation of TEOS catalyzed with DBTDL is k = 0.052 dm6 min-1 mol-1. From the determined condensation degree at the gelation point (0.20-0.35) and the ratio of consumed amount of ethoxysilane units to the consumed amount of monomer at the gelation point (0.49-0.69) it follows that the gel is predominantly formed by cross-linking of branched macromolecules, the reaction mixture containing no distinct proportions of polycyclic and highly condensed structural units. The density of network of the gel formed is relatively low, which was proved by 29Si CP/MAS NMR spectra of the solid gels. Investigation of QELS of the reaction mixture showed that the relatively large particles, microgels, were formed practically immediately after the reaction had started. The presence of such particles in the reaction mixture of acid catalyzed polycondensation of TEOS was not proved.

Keywords: Sol-gel polycondensation; Tetraethoxysilane; Dibutylbis[1-oxo(dodecyl)oxy]stannane; NMR, 1H, 29Si, 29Si CP/MAS; QELS.