Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes

Journal of the American Chemical Society

Volumn 118, Issue 35, 1996, Pages 8501-8502

  Loy, Douglas A ^a   Carpenter, Joseph P ^a   Myers, Sharon A ^a   Assink, Roger A ^a   Small, James H ^b   Greaves, John ^b   Shea, Kenneth J ^b  

^a SANDIA NATIONAL LABORATORIES   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOSILICON DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029812558     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961409k     Document Type: Article

References (21)

1. Review on hydrocarbon-bridged polysilsesquioxanes: Loy, D. A.; Shea, K. J. Chem. Rev. 1995, 95, 1431.
2. (a) Small, J. H.; Shea, K. J.; Loy, D. A. J. Non-Cryst. Solids 1993, 160, 234.
3. (b) Oviatt, H. W., Jr.; Shea, K. J.; Small, J. H. Chem. Mater. 1993, 5, 943.
4. (c) Loy, D. A.; Jamison, G. M.; Baugher, B. M.; Russick, E. M.; Assink, R. A.; Prabakar, S.; Shea, K. J. J. Non-Cryst. Solids 1995, 186, 44.
5. For a detailed discussion of the impact of cyclization reactions on sol-gel polymerizations see: (a) Ng, L. V.; Thompson, P.; Sanchez, J.; Macosko, C. W.; McCormick, A. V. Macromolecules 1995, 28, 6471.
6. (b) Sharp, K. G.; Michalczyk, M. J. J. Sol-Gel Sci. Technol. In press.
7. Osterholtz, F. D.; Pohl, E. R. J. Adhes. Sci. Technol. 1992, 6, 127.
8. 2O with (a) 10.8 mol % NaOH or (b) 10.8 mol % HCl as catalyst. It is significant to note that while bridged triethoxysilanes generally gel within a few hours at this concentration, organotriethoxysilanes or tetraethoxysilane will not gel until monomer concentrations exceed 1.4 M.
9. Illuminati, G.; Mandolini, L. Acc. Chem. Res. 1981, 14, 95.
10. (a) Rochow, E. G.; Gilliam, W. F. J. Am. Chem. Soc. 1941, 63, 798.
11. (b) Cypryk, M.; Sigwalt, P. Macromolecules 1994, 27, 6245.
12. (c) Sanchez, C; McCormick, A. V. J. Non-Cryst. Solids 1994, 167, 289.
13. M. G. Voronkov, Lavrentyev, V. I. Top. Curr. Chem., 1982, 102, 199 and references therein.
14. Solutions of 1 in ethanol (0.4 M) were mixed with 1 equiv of water (1 N HCl, 1.8 mol %) along with 15 mM chromium acetylacetonate and immediately placed into the spectrometer. Spectra were obtained every 10 min for several hours and again after 20 h.
15. Devreux, F.; Boilot, J. P.; Chaput, F.; Lecomte Phys. Rev. A 1990, 41, 41.
16. (a) Englehardt, G.; Jancke, H.; Magi, M.; Pehk, T.; Lippmaa, E. J. Organomet. Chem. 1971, 28, 293.
17. (b) Burton, D. J.; Harris, R. K.; Dodgson, K.; Fellow, C. J.; Semlyen, J. A. Polym. Commun. 1983, 24, 278-281.
18. (c) Seyferth, D.; Robison, J. Macromolecules 1993, 26, 407.
19. Chemical ionization mass spectrometry was performed with a VG Autospec using ammonia as the ionization gas. High-resolution mass spectra were obtained using a VG Autospec using isobutane or ammonia as the ionization gas. Solutions were prepared by dissolving monomer (0.4 M) in ethanol and adding 1 or 2 equiv of water (1 N HCl).
20. Ten-membered cyclic disilsesquioxanes observed in mass spectrometric studies of the sol-gel polymerization reactions of tetrakis(3-(triethoxysilyl)propyl)silane were recently reported by: Sharp, K. G.; Michalczyk, M. in the Hybrid Materials Symposium of the Inorganic Divsion at the 211th ACS National Meeting, New Orleans, LA, March 24-28, 1996; Michalczyk, M.; Simonsick, W. J.; Sharp, K. G. J. Organomet. Chem. In press.
21. Ten-membered cyclic disilsesquioxanes observed in mass spectrometric studies of the sol-gel polymerization reactions of tetrakis(3-(triethoxysilyl)propyl)silane were recently reported by: Sharp, K. G.; Michalczyk, M. in the Hybrid Materials Symposium of the Inorganic Divsion at the 211th ACS National Meeting, New Orleans, LA, March 24-28, 1996; Michalczyk, M.; Simonsick, W. J.; Sharp, K. G. J. Organomet. Chem. In press.