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Cluster-Crosslinked Inorganic-Organic Hybrid Polymers: Influence of the Cluster Type on the Materials Properties

  • Silvia Gross (a1), Vito Di Noto (a2), Guido Kickelbick (a1) and Ulrich Schubert (a1)


Methacrylate-substituted tetranuclear tantalum, zirconium and titanium oxide clusters (Zr4O2(OMc)12, Ti4O2(OPri)6(OMc)6, and Ta4O4(OEt)8(OMc)4) were prepared by reaction of the alkoxides with methacrylic acid. The clusters were then polymerized with methyl methacrylate as co-monomers in different molar ratios (0.5–2 mol% of the functionalized cluster). In the resulting inorganic-organic hybrid polymers, the clusters crosslink the polymer chains very efficiently. The physical properties and structural features of the hybrid polymers, investigated by their swelling behavior, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), 13C MAS NMR and impedance spectroscopy, exhibit a clear dependence on the cluster portion in the polymer and on the cluster type.



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1. Review articles: Sanchez, C., Ribot, F., New J. Chem. 18, 1007 (1994). D. A. Loy, K. J. Shea, Chem. Rev. 95, 1431 (1995). P. Judeinstein, C. Sanchez, J. Mater. Chem. 6, 511 (1996).
2. Review articles: Ribot, F., Sanchez, C., Comments Inorg. Chem. 20, 327 (1999). G. Kickelbick, U. Schubert, Monatsh. Chem. 132, 13 (2001). U. Schubert, Chem. Mater. 13, 3487 (2001). C. Sanchez, G. J. de A. A. Soler-Illia, F. Ribot, T. Lalot, C. R. Mayer, V. Cabuil, Chem. Mater. 13, 3061 (2001). G. Kickelbick, Progr. Polymer Sci., in press.
3. Review article: Schubert, U., Hüsing, N., Lorenz, A., Chem. Mater. 7, 2010 (1995).
4. Review articles: Harrison, P. G. J. Organometal. Chem. 542, 141 (1997). J. J. Schwab, J. D. Lichtenhan, Appl. Organomet. Chem. 12, 707 (1998).
5. Kickelbick, G. Schubert, U. Chem. Ber. 130, 473 (1997).
6. Trimmel, G. Gross, S. Kickelbick, G. Schubert, U. Appl. Organomet. Chem. 15, 401 (2001).
7. Gross, S. Kickelbick, G. Schubert, U. unpublished.
8. Moraru, B. Gross, S. Kickelbick, G. Trimmel, G. Schubert, U. Monatsh.Chem. 132, 993 (2001)
9. Schubert, U. Arpac, E. Glaubitt, W. Helmerich, A. Chau, C. Chem. Mater. 4, 291 (1992).
10. Moraru, B. Hüsing, N., Kickelbick, G. Schubert, U. Fratzl, P. Peterlik, H. Chem. Mater. 14 (2002) ASAP.
11. Kickelbick, G. Schubert, U. Eur. J. Inorg. Chem. 159 (1998).
12. Hubert-Pfalzgraf, L. G., Abada, V. Halut, S. Roziere, J. Polyhedron 16, 581 (1997).
13. Moraru, B. Kickelbick, G. Schubert, U. Eur. J. Inorg. Chem. 1295 (2001).
14. Trimmel, G. Fratzl, P. Schubert, U. Chem.Mater. 12, 602 (2000). U. Schubert, G. Trimmel, B. Moraru, W. Tesch, P. Fratzl, S. Gross, G. Kickelbick, N. Hüsing, Mat. Res. Soc. Symp. Proc. 628, CC2.3.1 (2001).
15. Schubert, U. Völkel, T., Moszner, N. Chem.Mater. 13, 3811 (2001).
16. An amount of 0.34 g (3.9 mmol) of methacrylic acid was added dropwise under stirring to a solution of 0.54 g (1.35 mmol) of Ta(OEt)5 in 3 ml benzene under an argon atmosphere. The solution was strirred at room temperature for 5 h and was then stored at 4C for 25 d, resulting in the separation of colorless crystals (yield: 60%). Elemental analysis: found (calcd): C 25.8 (25.7); Ta 48.9 (48.3); H 3.8 (4.6).
17. Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge C82 1EZ, UK [fax int. code +(1223) 336-033, e-mail:] quoting the depository number CCDC 181001.
18. A typical procedure is as follows: To a solution of 4.25 g (42.5 mmol) methyl methacrylate (filtered over alumina to remove the stabilizer) and 1.23 g (0.83 mmol) of Ta4 in 2.2 ml toluene in an argon atmosphere, 45 mg (0.19 mmol) of dibenzoylperoxide were added. The mixture was heated to 60°C for 16 h, during which it solidified. The solvent was then removed in vacuo and the residual toulene extracted by washing with ethyl acetate twice. The solvent was again removed under reduced pressure. The olefin: initiator: solvent ratio was kept constant when the cluster: olefin ratio was varied. Elemental analyses for samples with 2, 1, and 0.5 mol% of cluster corresponded very well to the calculated values, i.e. the polymers were essentially solvent-free after this procedure.
19. Kickelbick, G. Feth, M. P. Bertagnolli, H. Moraru, B. Trimmel, G. Schubert, U. Monatsh. Chem. 133 (2002), in press.
20. Wall, L. A. Soc.Plastics Engs. J. 16, 810 (1960). R. Simha, Adv. Chem. Ser. 34, 157 (1962).
21. Noto, V. Di, Vittadello, M. Lavina, S. Fauri, M. Biscazzo, S. J. Phys. Chem. B 105, 4584 (2001).
22. Gross, S. Trimmel, G. Schubert, U. Noto, V. Di, Polym. Adv. Technol. 12, 1 (2001).

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Cluster-Crosslinked Inorganic-Organic Hybrid Polymers: Influence of the Cluster Type on the Materials Properties

  • Silvia Gross (a1), Vito Di Noto (a2), Guido Kickelbick (a1) and Ulrich Schubert (a1)


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