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The Catalytic Synthesis of Inorganic Polymers for High Temperature Applications and as Ceramic Precursors

Published online by Cambridge University Press:  21 February 2011

Jeffrey A. Rahn ,
Richard M. Laine  and
Zhi-Fan Zhang
Jeffrey A. Rahn
Affiliation:
Contribution from the Department of Materials Science and Engineering and the Polymeric Materials Program of the Washington Technology Center, University of Washington, Seattle, WA 98195
Richard M. Laine
Affiliation:
Contribution from the Department of Materials Science and Engineering and the Polymeric Materials Program of the Washington Technology Center, University of Washington, Seattle, WA 98195
Zhi-Fan Zhang
Affiliation:
Contribution from the Department of Materials Science and Engineering and the Polymeric Materials Program of the Washington Technology Center, University of Washington, Seattle, WA 98195
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Polysilsesquioxanes,-[RSi(O)1.5 ]x-, exhibit many properties that are potentially quite useful for industrial applications. These properties include high temperature stability (−600°C in O2); good adhesion and, liquid crystal-like behavior for some derivatives. Moreover, [MeSi(O)l.5]x, polymethylsilsesquioxane has been used successfully as a precursor for the fabrication of carbon fiber/“black glass” (SiO2/SiC/C) composites and “black glass” fibers.

Current methods of preparation depend on hydrolysis of RSiCl3 or RSi(OR)3. Unfortunately, this approach leads to several products that are difficult to purify because polysilsesquioxanes exhibit a great propensity for forming gels. We describe here a simple catalytic approach to the synthesis of polymethylsilsesquioxane copolymers of the type -[MeRSiO].3[MeSi(O)1.5].7- where R - H, OMe, OEt, OnPr and OnBu. The R - H copolymer is produced by catalytic redistribution of -[MeHSiO]xoligomers using dimethyltitanocene, Cp2TiMe2 as the catalyst precursor.

Following catalytic redistribution, the resulting copolymer, -[MeHSiO].3[MeSi(O)1.5].7−, is reacted in situ with alcohols to produce -[Me(R'O)SiO].3[MeSi(0)1.5].7− (where R' - Me, Et, nPr and nBu) which serve as masked forms of the polymethylsilsesquioxane. These new copolymers have been characterized by 1H, 13C and 29Si NMR TGA and DTA. The NMR studies allow us to assign structures for the copolymer.

These new copolymers exhibit improved tractability. Their high temperature properties are all quite similar; although, the MeO-, EtO- and especially the nPrO- derivatives give much higher ceramic yields than expected.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 171: Symposium O – Polymer Based Molecular Composites , 1989 , 31
Copyright
Copyright © Materials Research Society 1990

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References

REFERENCES

1. a. Voronkov, M. G., Lavrent'yev, V. I., Top. Curr. Chem. 12, 199 (1982). b. C. L. Frye, J. M. Klosowski, J. Am. Chem. Soc., 93, 4599 (1971).Google Scholar
2. Laine, R. M., Rahn, J.A., Youngdahl, K. A., Babonneau, F., Harrod, J. F. submitted to Chem. Mat.Google Scholar
3. See for example: a. January, J. R.; U. S. Patent No. 4,472,510. b. S. Uchimara, Eur. Pat. Appl. EP 312,280--CA 111:156040j. c. H. Adachi, E. Adachi, O. Hayashi, K. Okabashi, Jpn. Kok. Tokk. Koho JP 01 92,224.Google Scholar
4. a. White, D. A., Oleff, S. M., Boyer, R. D., Budringer, P. A., Fox, J. R., Adv. Cer. Mat., 2, 45 (1987). b. D. A. White, S. M. Oleff, J. R. Fox, ibid p. 53.Google Scholar
5. a. Baney, R. in Ultrastructure Processing of Ceramics. Glasses, and Composites, edited by Hench, L. L. and Ulrich, D. R., (Wiley-lnterscience, 1984) pp 245–255. b. H. Zhang and C. Pantano in “Proceedings of the Fourth Internat. Confer. on Ultrastruct. of Ceramics. Glasses and Composites, edited by D. Uhlmann and D. R. Ulrich 1989, in press.Google Scholar
6. Kamiya, K., Makoto, O., Yoko, T., J. Noncryst. Sol.; 83, 208 (1986).Google Scholar
7. a. Harrod, J. F., Xin, S., Aitken, C., Mu, Y., and Samuel, E., International Conference on Silicon Chemistry, June,1986; St. Louis, Mo. b. J. F. Harrod, S. Xin, C. Aitken, Y. Mu, E. Samuel, submitted to Can. J. Chem. c. For a review on transition metal catalyzed synthesis of inorganic polymers see:, R. M. Laine in Aspects of Homogeneous Catalysis, edited by R. Ugo (Kluwer pub., Dordrecht, 1989) vol 7, in press.Google Scholar
8. Youngdahl, K. A., Hoppe, M. L., Laine, R. M., Rahn, J. A., and Harrod, J. F., “Proceedings of the 4th Internat. Confer. on Ultrastruct. of Ceramics. Glasses and Composites, edited by Uhlmann, D. and Ulrich, D. R. (Wiley-Interscience, 1989) in press.Google Scholar
9. Laine, R. M., Zhang, Z.-F. and Rahn, J. A. unpublished results. Detailed experimental results will be reported elsewhere.Google Scholar
10. Luo, X-L. and Crabtree, R. H., J. Am. Chem. Soc. 111, 2527 (1989).Google Scholar
11. a. Marsmann, H. and Kintzinger, J. P. in Oxygen 17 and Silicon 29 NMR. (Springer-Verlag, 1981) New York pp 74–239. b. E. A. Williams in Ihe Chemistry of Organic Silicon Compounds, edited by S. Patai and Z. Rappoport (John-Wiley and Sons, 1989) pp 512-554.Google Scholar
12. a. Handbook of Chemistry and Physics. CRC Co. (Chemical Rubber Co. 64th Ed.) p F–193. b. R. Walsh in The Chemistry of Organic Silicon Compounds. edited by S. Patai and Z. Rappoport (John-Wiley and Sons, 1989) pp 371-392 and references therein.Google Scholar