Abstract
Catalytic cross-dehydrocoupling polymerization of phenylsilane (1) with water was investigated. Among transition metal derivatives investigated, Pd2(dba)3 is the most active catalyst for the polymerization, which affords a high molecular weight polymer (P1) soluble in common organic solvents (Mw/Mn = 62200/25400). The polymer can be cast into a film. The polymerization was monitored by SEC and 29Si NMR. It was shown that hydrolysis of SiH and cross-dehydrocoupling reaction between SiH and SiOH are faster compared to dehydration of SiOH in this polymerization, and plausible reaction mechanism was suggested. Chemical structure and thermal property of P1 was characterized by NMR, IR, and TGA.
Similar content being viewed by others
Article PDF
References
R. G. Jones, W. Ando, and J. Chojnowski Ed., “Silicon-Containg Polymer”, 2000, p 157.
R. H. Baney, M. Itoh, A. Sakakibara, and T. Suzuki, Chem. Rev., 95, 1409 (1995).
D. A. Loy and K. J. Shea, Chem. Rev., 95, 1431 (1995).
A. Provatas and J. G. Matisons, Trends in Polym. Sci., 5, 327 (1997).
M. M. Sprung and F. O. Guenther, J. Polym. Sci., 28, 17 (1958).
J. F. Brown, L. H. Vogt, A. Katchman, J. W. Eustance, K. M. Kiser, and K. W. Krantz, J. Am. Chem. Soc., 82, 6194 (1960).
K. A. Andrianov, G. A. Kurakov, F. F. Sushentsova, V. A. Myagkov, and V. A. Avilov, Vysokomol. Soyed., 7, 1477 (1965).
S. A. Pavlova, V. I. Pakhomov, and I. I. Tverdokhlebova., Vysokomol. Soyed., 6, 1275 (1964).
E. C. Lee and Y. Kimura, Polym. J., 29, 678 (1997).
E. C. Lee and Y. Kimura, Polym. J., 30, 234 (1998.
Y. Li and Y. Kawakami, Macromolecules, 32, 3540 (1999).
Y. Li and Y. Kawakami, Macromolecules, 32, 6871 (1999).
Y. Li and Y. Kawakami, Macromolecules, 32, 8768 (1999).
G. Engelhardt, M. Maegi, and E. Lippmaa, J. Organomet. Chem., 54, 115 (1973).
L. Guizhi, S. Lianghe, and Y. Meiling, Chin. J. Polym. Sci., 14, 41 (1996).
K. J. Shea, D. A. Loy, and O. Webster, J. Am. Chem. Soc., 114, 6700 (1992).
Selected spectroscopic data: PhSiH (Me3SiO)2: 1H NMR (300 MHz, CDCl3): δ 0.14 (s, 18 H, SiCH3), 4.97 (s, 1 H, SiH), 7.34–7.46 (m, 3 H, Ph), 7.53–7.60 (m, 2 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 1.72, 127.76, 130.00, 133.10, 137.02. 29Si NMR (95.5 MHz, CDCl3): δ -49.38, 10.77. MS (EI, m/z): 283 ([M-H]+), 269 ([M–Me]+). PhSi(Me3SiO)3: 1H NMR (300 MHz, CDCl3): δ 0.11 (s, 27 H, SiCH3), 7.29–7.41 (m, 3 H, Ph), 7.52–7.58 (m, 2 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 1.60, 127.60, 129.58, 133.93, 135.64. 29Si NMR (95.5 MHz, CDCl3): δ -77.81, 8.83. MS (EI, m/z): 357 ([M–Me]+).
(Me3SiO)2PhSiOSiPhH(OSiMe3): 1H NMR (300 MHz, CDCl3): δ 0.072, 0.079, 0.087 (3 s, 27 H, SiCH3), 5.05 (s, 1 H, SiH), 7.28–7.45 (m, 6 H, Ph), 7.54–7.60 (m, 4 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 1.66, 127.54, 127.69, 129.68, 130.07, 133.27, 133.89, 134.60, 136.40. 29Si NMR (95.5 MHz, CDCl3): δ -78.42, -49.87, 9.52, 11.11. MS (EI, m/z): 494 ([M]+). {(Me3SiO)2PhSi}2O: 1H NMR (300 MHz, CDCl3): δ 0.07 (s, 36 H, SiCH3), 7.28–7.45 (m, 6 H, Ph), 7.53–7.59 (m, 4 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 1.67, 127.40, 129.51, 133.98, 134.90. 29Si NMR (95.5 MHz, CDCl3): δ -79.79, 9.08. MS (EI, m/z): 567 ([M–Me]+). {(Me3SiO)PhSiO}3: 1H NMR (300 MHz, CDCl3): δ -0.034, 0.084, 0.203 (3 s, 27 H, SiCH3), 7.18–7.50 (m, 9 H, Ph), 7.58–7.64 (m, 4 H, Ph), 7.74–7.79 (m, 2 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 1.38, 1.55, 1.73, 127.58, 127.62, 127.66, 130.12, 130.21, 130.32, 132.44, 132.58, 132.75, 133.92, 134.03, 134.09. 29Si NMR (95.5 MHz, CDCl3): δ -70.85, -70.56, -70.45, 11.26, 11.33, 11.46. MS (EI, m/z): 615 ([M–Me]+). (PhCH2CH2)2C = O: 1H NMR (300 MHz, CDCl3): δ 2.71 (t, 4 H, PhCH2CH2, J = 7.8 Hz), 2.89 (t, 4 H, PhCH2, J = 8.1 Hz), 7.14–7.22 (m, 6 H, Ph), 7.24–7.31 (m, 4 H, Ph). 13C NMR (125.5 MHz, CDCl3): δ 29.71, 44.50, 126.10, 128.29, 128.48, 140.99, 209.11. MS (EI, m/z): 238 ([M]+).
Reaction condition: 0.250 mmol of 1, 0.375 mmol of water, and 0.001 mmol of Pd2(dba)3 in 0.05 mL THF.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Seino, M., Imae, I. & Kawakami, Y. Catalytic Cross-Dehydrocoupling Polymerization of Phenylsilane with Water. A New Approach to Poly(phenylsilsesquioxane). Polym J 35, 197–202 (2003). https://doi.org/10.1295/polymj.35.197
Issue Date:
DOI: https://doi.org/10.1295/polymj.35.197