Abstract
The investigation of the effects of small amounts of Ti-, Zr-, Al-, Sn- and Si-alkoxides and those of triethylamine and hydrochloric acid on the condensation reaction of diphenylsiloxanediol (DPSD) in molar ratio Si : additive = 1:0.01 and 1:0.04 by 29Si NMR shows a decrease in their activity in the order Ti≈HCl>Al>Sn≈N(Et)3≈Zr>Si after 6 h reaction time. The influence of the type of alkoxide ligands attached to the metal on the condensation rate of DPSD was found relatively low compared to the different metals. In presence of Ti-alkoxide the condensation reaction of DPSD leads to di-, tri- and tetrasiloxanediols, the latter of which dominates and crystallizes from the solution as octaphenyltetrasiloxanediol. The catalysis of DPSD solutions by Al-alkoxide and HCl results preferably in tetraphenyldisiloxanediol species even after a few days. The complexity of metal alkoxides and the hydrolytic stability of heterometallic Si−O−M bonds have been discussed as possible reasons for the differences in the catalytic activity of the metal alkoxide.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
K.A. Andrianov, S.V. Pitschadse, and V.V. Komarova, Izv. Akad. Nauk SSSR, Ser. Chimija, 261–264 (1962).
Sol-Gel Technology for Thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by L.C. Klein (Noyes Publications, Park Ridge, New Jersey, 1988).
H.Schmidt, J. Non-Cryst. Solids 100, 51–64 (1988).
R.C.Mehrotra, Chemistry, Spectroscopy and Application of Sol-Gel Glasses, edited by R.Reisfeld, C.K.Jorgensen (Springer-Verlag, Berlin, Heidelberg, 1992).
M.Emili, L.Incoccia, S.Mobilio, G.Fagherazzi, and M.Guglielmi, J. Non-Cryst. Solids 74, 129–146 (1985).
S.Dire, F.Babonneau, C.Sanchez, and J.Livage, J. Mater. Chem. 2, 239 (1992).
S.Dire, F.Babonneau, G.Cartuan, and J.Livage, J. Non-Cryst. Solids 147/148, 62–66 (1992).
G.Philipp and H.Schmidt, J. Non-Cryst. Solids 63, 283–292 (1984).
W.Noll, Chemie und Technologie der Silicone (Verlag Chemie, Weinheim, 1968).
D.C. Bradley and C. Prevedorou-Demas, Chemistry and Industry, 1659 (1970).
K. Ito, K. Imai, and K. Kumagae, JP 53147798 (1978).
S.Dire and F.Babonneau, J. Non.-Cryst. Solids 167, 29–36 (1994).
D.C.Bradley, R.C.Mehrotra, and D.P.Gaur, Metal Alkoxides (Academic Press, London, 1978).
J.D.Basil and C.C.Lin, Ultrastructure Processing of Advanced Ceramics, edited by J.D.Mackenzie and D.R.Ulrich (Wiley, New York, 1988), pp. 783–794.
H.C.Marsmann, Chemiker Ztg. 96, 288–289 (1972).
D.Becker, J.A.Ferretti, and P.N.Gambhir, Anal. Chem. 51, 1413–1420 (1979).
G.Engelhardt, M.Mägi, and E.Lippmaa, J. Organomet. Chem. 54, 115–122 (1973).
E.A.Williams, J.D.Cargioli, and R.W.Larochelle, J. Organomet. Chem. 108, 153–158 (1976).
D.Hoebbel, T.Reinert, and H.Schmidt, J. Sol-Gel Science and Technology 6, 139–149 (1996).
F.Babonneau, Mat. Res. Soc. Symp. Proc. 346, 949 (1994).
R.L. Martin and G. Winter, J. Chem. Soc., 2947 (1961).
C.G. Barraclough, R.L. Martin, and G. Winter, J. Chem. Soc., 758 (1964).
D.C.Bradley and C.E.Holloway, Inorg. Chem. 3, 1163 (1964).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hoebbel, D., Reinert, T. & Schmidt, H. 29Si NMR investigation of condensation reactions of diphenylsilanediol in presence of Ti-, Zr-, Al-, Sn- and Si-alkoxides. J Sol-Gel Sci Technol 7, 217–224 (1996). https://doi.org/10.1007/BF00401040
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00401040