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Hybrid Styryl-Based Polyhedral Oligomeric Silsesquioxane (Poss) Polymers

  • T. S. Haddad (a1), E. Choe (a2) and J. D. Lichtenhan (a2)


We have taken a unique approach to the synthesis and study of hybrid organic/inorganic materials. Our method involves synthesizing nano-size inorganic P1R7Si8Ol2 clusters which contain seven inert “R” groups for solubility and only one functional “P” group for polymerization. This strategy permits the synthesis of melt processable, linear hybrid polymers containing pendent inorganic clusters and allows us to study the effect these clusters have on chain motions and polymer properties. The synthesis of styrene-based polyhedral oligomeric silsesquioxane (POSS) macromers, their free radical homopolymerization and copolymerizations with varying amounts of 4-methylstyrene, and analysis of the effect of the pendent POSS group is presented. All of these polymers decompose under nitrogen between 365 and 400 °C, and the glass transitions for these materials vary from around 110 °C up to the decomposition point. Both Tdec and Tg increase with increasing POSS content. The shorter the spacer unit between the POSS group and the polymer chain the higher the Tg. Interestingly, a slight change in the inert “R” groups on the POSS cluster has a large effect on the glass transition indicating that POSS-POSS interactions have an effect on chain mobility.



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1. Reviews and leading references for recent progress in hybrid materials are: (a) Hybrid Organic-Inorganic Composites, edited by Mark, J.E., Lee, C.Y-C. and Bianconi, P.A., (ACS Symposium Series 585, American Chemical Society: Washington DC 1995).(b) L. Mascia, Trends Polym. Sci. 3, 61 (1995). (c) C. Sanchez and F. Ribot, Nouv. J. Chem. 18, 1007 (1994).
2. The diameter swept out by a R8Si8O12 POSS molecule is approximately 15 A with an inner Si-Si diameter of 5.4 A. (a) Larsson, K., Kemi, Ark., 16, 203 (1960).(b) F.J. Feher and T.A. Budzichowski, J. Organomet. Chem. 373, 153 (1989). (c) T.P.E. Auf der Hyde, H.-B. Burgi, H. Burgy and K.W. Tornroos, Chimia, 45, 38 (1991)
3. (a) Lichtenhan, J.D., Vu, N.Q., Carter, J.A., Gilman, J.W. and Feher, F.J., Macromolecules, 26, 2141, (1993).(b) J.D. Lichtenhan, Comments Inorg. Chem. 17, 115 (1995). (c) T.S. Haddad and J.D. Lichtenhan, J. Inorg. Organomet. Polym. 5, 237 (1995). (d) J.D. Lichtenhan, Y.A. Otonari and M.J. Carr, Macromolecules 28, 8435 (1995). (e) R. Mantz, P.F. Jones, K.P. Chaffee, J.D. Lichtenhan, J.W. Gilman, I. Ismail and M.J. Burmeister, Chem Mater. in press (1996).
4. (a) Feher, F.J., Newman, D.A. and Walzer, J.F., J. Am. Chem. Soc. 111, 1741 (1989). (b) F.J. Feher, T.A. Budzichowski, R.L. Blanski, K.J. Weller and J.W. Ziller, Organometallics 10, 2526 (1991). (c)J.F. Brown Jr. and L.H. Vogt Jr. J. Am. Chem. Soc. 87, 4313 (1965).
5. Isolated yields were: 2a (97 %), 2b (95 %), 2c (78 %), 2d (87 %).
6.. For a discussion on elastomeric phase-separated triblock polymers see Odian, G. Principles of Polymerization (J. Wiley & Sons: New York, 1991) pp. 148149, 426.

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Hybrid Styryl-Based Polyhedral Oligomeric Silsesquioxane (Poss) Polymers

  • T. S. Haddad (a1), E. Choe (a2) and J. D. Lichtenhan (a2)


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