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Star Gels. New Hybrid Network Materials from Polyfunctional Single Component Precursors

Published online by Cambridge University Press:  10 February 2011

Kenneth G. Sharp
Affiliation:
Central Research, DuPont Co., Wilmington, DE, 19880-0323 U.S.A.
Michael J. Michalczyk
Affiliation:
Central Research, DuPont Co., Wilmington, DE, 19880-0323 U.S.A.
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Abstract

A new family of hybrid inorganic/organic network materials – the star gels – has been synthesized from single component molecular precursors. The starting materials comprise an organic core with multiple flexible arms which terminate in network-forming trialkoxysilane groups. The core can be a single silicon atom, linear disiloxane segment or ring system. With at least 12 alkoxysilane groups per molecule, gelation rates in aqueous or formic acid media can be extremely high, but can be attenuated several orders of magnitude by choice of solvent system. The degree of intramolecular condensation of these molecules has been assessed via mass spectrometric techniques. Transparent glasses which show brittle fracture but high levels of toughness have been generated from this family of precursors. The materials do not show plastic deformation even under compressive stress of 350 MPa. No evidence for open porosity in the glasses has been obtained. The organic content of the networks can be increased by lengthening the arms; the inorganic content can be increased via co-hydrolysis with simple tetraalkoxysilanes such as TEOS. Species with longer arms lead to glasses with higher coefficients of thermal expansion.

Type
Research Article
Copyright
Copyright © Materials Research Society 1996

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References

1. Mark, J. E., Heterog. Chem. Rev., in pressGoogle Scholar
2. Shea, K. J., Loy, D. A., Webster, O. W., Chem. Mater 1, 572–4 (1989).Google Scholar
3. Shea, K. J., Loy, D. A., Webster, O. W., Polym. Mater. Sci. Eng 63, 281–5 (1990).Google Scholar
4. Loy, D. A., Shea, K. J., Russick, E. M.. Preparation of aryl-bridged polysilsesquioxane aerogels, in Mater. Res. Soc. Symp. Proc; Hampden-Smith, M., Klemperer, W., Brinker, C. J., Eds., 1992; Vol.271; pp. 699704.Google Scholar
5. Shea, K. J., Loy, D. A., Webster, O., J. Am. Chem. Soc 114, 6700–10 (1992).Google Scholar
6. Corriu, R. J. P., Moreau, J. J. E., Thepot, P., Man, M. Wong Chi, Chorro, C., Lere-Porte, J.-P., Sauvajol, J.- L., Chem. Mater. 6, 640–9 (1994).Google Scholar
7. Small, J. H., Shea, K. J., Loy, D. A., J. Non Cryst. Solids 160, 234–46 (1993).Google Scholar
8. Oviatt, H. W. Jr., Shea, K. J., Small, J. H., Chem. Mater 5, 943–50 (1993).Google Scholar
9. In some cases, the yield is somewhat improved if trichlorosilane is used in the hydrosilylation, then the chlorosilane is alkoxylated in a second step.Google Scholar
10. The Pt catalyst of choice was Pt((ViMe2Si) 2O) [Karstedt's catalyst]; concentrations of about 20 ppm by weight were found effective. Caution should be used since hydrosilylation conducted without solvent can be highly exothermic. Soluble catalyst residues were typically removed with activated charcoal.Google Scholar
11. Simonsick, W. J.. Characterization of Polymer Building Blocks by K+ Ionization of Desorbed Species. In Structure-Property Relationships in Polymers; Urban, Craver, M. W.;, , C. D. Eds.; American Chemical Society: Washington, D.C., 1993; Vol.236.Google Scholar
12. Woignier, T., Phalippou, J., J. Non-cryst. Solids 93, 17 (1987).Google Scholar
13. Brinker, C. J., Scherer, G. W. Sol-gel Science; Academic Press: San Diego, CA, 1990.Google Scholar
14. Sharp, K. G., J. Sol-gel Sci. Tech. 2, 35 (1994).Google Scholar
15. Schmidt, H., J. Non Cryst. Solids 73, 681–91 (1985).Google Scholar
16. Gottardi, V., Guglielmi, M., Bertoluzza, A., Fagnano, C., Morelli, M. A., J. Non-Cryst. Solids 63, 7180 (1984).Google Scholar
17. Colby, M. W., Osaka, A., Mackenzie, J. D., J. Non-Cryst. Solids 99, 129–39 (1988).Google Scholar
18. Kinloch, A. J., Young, R. J. Fracture Behavior of Polymers; Applied Science Publishers: Essex, England, 1983.Google Scholar
19. Fahrenholtz, W. G., Smith, D. M., Hua, D. W., J. Non-Cryst. Solids 144, 4552 (1992).Google Scholar
20. Several reports now exist of silica gel which shows no appreciable nitrogen adsorption at 77 °K over several hours but does adsorb CO 2 at higher temperatures.Google Scholar