Turgay SEÇKİN, Süleyman KÖYTEPE, İsmail ÖZDEMİR, Bekir ÇETİNKAYA

Synthesis of a Ruthenium Complex Bound to a Polyimide Matrix: Investigating the Catalytic Properties in a Hydrosilylation Reaction

3,6-Bis(dimethylamino)acridine(hexamethylbenzene)dichlororuthenium(II) was used as a tricyclic heteroatomic monomer to prepare polyimides from the corresponding dianhyrides by solution condensation. The ruthenium complex monomer was synthesized starting from [RuCl2(HMB)]2 and 3-6-bis(dimethylamino)acridine. The polymers had inherent viscosities of 1.77 to 2.11 and were soluble in most polar solvents. The glass transition temperatures were in the range of 204 to 298 °C and the 10% weight loss in the range of 506-626 °C, depending upon the structure of the dianhyride monomer. The catalytic activity of the polyimides tested in a hydrosilylation reaction of acetophenone was up to 90%. Leaching of ruthenium into the reaction mixture, found to be in the range of 60-75 ppm, was an indication of reduced catalyst bleeding.

Anahtar Kelimeler:

Heterogeneous catalysis, Ruthenium, Polyimide, Hydrosilylation

Synthesis of a Ruthenium Complex Bound to a Polyimide Matrix: Investigating the Catalytic Properties in a Hydrosilylation Reaction

Keywords:

Heterogeneous catalysis, Ruthenium, Polyimide, Hydrosilylation,

PDF

___

B. Marcinies, “Comprehensive Handbook on Hydrosilylation” Pergamon Press, London 1992.
L.H. Sommer, E.W. Peietrusza and F.C. Whitmore, J. Am. Chem. Soc. 69, 188-189 (1947).
J.L. Speier, J.A. Webster and G.H. Barnes, J. Am. Chem. Soc. 79, 974-979 (1957).
J.L. Speier, Adv. Organomet. Chem. 17, 407-447 (1979).
B.D.S. Karstedt, General Electric Co., USP 226928, 1972.
Y. Seki, K. Takeshita, K. Kawamato, S. Murai and N. Sonoda, J. Org. Chem. 51, 3890-3895 (1986).
F. Kakuichi, Y. Tanaka, N. Chatani and S. Murai, J. Organomet. Chem. 456, 45-47 (1993).
R. Takeuchi and H. Yasue, Organometallics, 15, 2098-2102 (1996).
A.M. Lapointe, F.C. Rix and M. Brookhart, J. Am. Chem. Soc. 119, 906-917 (1997).
P. Steffanut, J.A. Osborne, A. Decain and J. Fisher, Chem. Eur. J. 4, 2008-2017 (1998).
S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda and N. Chatani. Nature, 366, 529-531 (1993).
T. Se¸ckin, S. Koytepe, ˙I. ¨Ozdemir, N. G¨urb¨uz and B. C¸ etinkaya, J. Inorg. Organomet. P. 14, 177-190 (2004).
B. Marciniec, Silicon Chemistry, 1, 155-175 (2002).
R. Dralce, R. Dunn, D.C. Sherrington and S.J. Thomson, Chem. Commun. 1931-1932 (2000).
Z.M. Michalsca, K. Strzelec and J.W. Sobczak, J. Mol. Catal. A-Chem. 156, 91-102 (2000).
A. Carmona, A. Corma, M. Iglesias, A. San. Jose and F. Sanchez, J. Organomet. Chem. 492, 11-21 (1995).
J.O. Krause, S. Lubdad, O. Nuken and M. Buchmeiser, Adv. Synth. Catal. 345, 996-1004 (2003).
K.L. Mittal, “Polyimides: Synthesis, characterization and applications” Vols. 1 & 2, Plenum, New York, 1984.
M.K. Ghosh and K.L. Mittal, “Polyimides: Fundamentals and Applications” Marcel Dekker, New York, D. Wilson, H.D. Stenzenberger and P.M. Hergenrother, “Polyimides” Blackie, Glasgow, 1990.
T. Seckin, S. Koytepe, S. Demir, I. ¨Ozdemir and B. Centinkaya, J. Inorg. Organomet. P. 13, 223-235 (2003).
C.P. Yang, Y.Y. Su and F.Z. Hsiao, Polymer 45, 7529-7538 (2004).
T. Seckin, S. Koytepe, I. ¨Ozdemir, B. Cetinkaya, J. Inorg. Organomet. P., 13, 9-20 (2003).
Ha. Yagci and L.J. Mathias, Polymer, 39, 3779-3786 (1998).
T. Seckin, I. ¨Ozdemir, B. Cetinkaya and S. Koytepe, J. Mol. Catal. A-Chem., 179, 263-270 (2002).
K.U. Jeong, J.J. Kim and T.H. Yoon, Polymer 42, 6019-6030 (2001).
R.H. Vora, S.H. Goh and T.S. Chung, Polymer Eng. Sci. 40, 1318-1329 (2000).
D.S. Reddy, C.F. Shu and F.I. Wu, J. Polym. Sci. Pol. Chem. 40, 262-268 (2002).
J.G. Liu, M.H. He, H.W. Zhou, Z.G. Qian, F.S. Wang and S.Y. Yang, J. Polym. Sci. Pol. Chem. 40, 119 (2002).
S.H. Hsiao and W.T. Chen, J. Polym. Res. 10, 95-103 (2003).