29Si NMR study on co-hydrolysis processes in Si(OEt)4–RSi(OEt)3 –EtOH–water–HCl systems (R=Me, Ph): effect of R groups

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Yoshiyuki Sugahara, Tsuyoshi Inoue and Kazuyuki Kuroda


Abstract

Hydrolysis and initial polycondensation processes in the Si(OEt)4 (TEOS)–RSi(OEt)3 –EtOH–water–HCl systems (R=Me, Ph) [TEOS:RSi(OEt)3:EtOH:water:HCl=1:1:24:x:y (x=12, 2/3; y=2×10-3 , 4×10-3 , 8×10-2 )] have been investigated by using 29Si NMR spectroscopy. For comparison, the alkoxysilanes [TEOS, MeSi(OEt)3 (MTES), PhSi(OEt)3 (PTES)] were hydrolysed separately in a similar manner. In a water-rich TEOS–MTES system (water:Si=12:1), a silanol-terminated codimer [Me(HO)2SiOSi(OH)3 ] was detected as well as (HO)3SiOSi(OH)3 and Me(HO)2SiOSi(OH)2Me, suggesting that the hydrolysed monomers were condensed rather randomly. In contrast, in a water-rich TEOS–PTES system, hydrolysed monomers derived from TEOS and those from PTES were condensed independently; a silanol-terminated codimer [Ph(HO)2SiOSi(OH)3 ] did not form, and only (HO)3SiOSi(OH)3 and Ph(HO)2SiOSi(OH)2Ph were detected. These observations in the TEOS–PTES system suggest the presence of the association of the phenyl groups. In water-restricted systems (water:Si=1:3), monomers were only partially hydrolysed, and ethoxy-terminated codimers [R(EtO)2SiOSi(OEt)3 (R=Me, Ph)] formed in both the TEOS–MTES and the TEOS–PTES systems.


References

  1. H. Schmidt, J. Non-Cryst. Solids, 1985, 73, 681 CrossRef CAS.
  2. H. K. Schmidt, ACS Symp. Ser., 1988, 360, 333 CAS.
  3. H. K. Schmidt, Mater. Res. Soc. Symp. Proc., 1990, 180, 961 CAS.
  4. G. L. Wilkes, B. Orler and H. H. Huang, Polym. Prepr., 1985, 26, 300 Search PubMed.
  5. H. H. Huang, B. Orler and G. L. Wilkes, Polym. Bull., 1985, 14, 557 CrossRef CAS.
  6. H. H. Hsin, B. Orler and G. L. Wilkes, Macromolecules, 1987, 20, 1322 CrossRef CAS.
  7. U. Schubert, N. Hüsing and A. Lorenz, Chem. Mater., 1995, 7, 2010 CrossRef CAS.
  8. B. M. Novak, Adv. Mater., 1993, 5, 422 CrossRef CAS.
  9. A. Morikawa, Y. Iyoku, M. Kakimoto and Y. Imai, J. Mater. Chem., 1992, 2, 679 RSC.
  10. N. Nishiyama, K. Horie and T. Asakura, J. Appl. Polym. Sci., 1987, 34, 1619 CrossRef CAS.
  11. F. Babonneau, K. Thorne and J. D. Mackenzie, Chem. Mater., 1989, 1, 554 CrossRef CAS.
  12. Y. T. Lee, K. Iwamoto, H. Sekimoto and M. Seno, J. Membr. Sci., 1989, 42, 169 CrossRef CAS.
  13. R. H. Glaser, G. L. Wilkes and C. E. Bronnimann, J. Non-Cryst. Solids, 1989, 113, 73 CrossRef CAS.
  14. M. P. Besland, C. Guizard, N. Hovnanian, A. Larbot, L. Cot, J. Sanz, I. Sobrados and M. Gregorkiewitz, J. Am. Chem. Soc., 1991, 113, 1982 CrossRef CAS.
  15. W. G. Fahrenholts, D. M. Smith and D.-W. Hua, J. Non-Cryst. Solids, 1992, 144, 45.
  16. F. Babonneau, L. Bois and J. Livage, Mater. Res. Soc. Symp. Proc., 1992, 271, 237 CAS.
  17. F. Babonneau, L. Bois, J. Maquet and J. Livage, Eur. Mater. Res. Monogr., 1992, 5, 319 Search PubMed.
  18. C. A. Fyfe, Y. Zhang and P. Aroca, J. Am. Chem. Soc., 1992, 114, 3252 CrossRef CAS.
  19. M. P. J. Peeters, W. J. J. Wakelkamp and A. P. M. Kentgens, J. Non-Cryst. Solids, 1995, 189, 77 CrossRef CAS.
  20. M. Smaihi, T. Jermoumi and J. Marignan, Chem. Mater., 1995, 7, 2293 CrossRef CAS.
  21. C. J. Brinker and G. W. Scherer, Sol–Gel Science, Academic Press, San Diego, 1990, pp. 152–174 Search PubMed.
  22. K. A. Smith, Macromolecules, 1987, 20, 2514 CrossRef CAS.
  23. F. Devreux, J. P. Boilot, F. Chaput and A. Lecomte, Phys. Rev. A, 1990, 41, 6901 CrossRef CAS.
  24. R. Nass, E. Arpac, W. Glaubitt and H. Schmidt, J. Non-Cryst. Solids, 1990, 121, 370 CrossRef CAS.
  25. D. Hoebbel, I. Pitsch, H. Jancke and B. Costisella, Z. Anorg. Allg. Chem., 1990, 588, 199 CrossRef CAS.
  26. I. Hasegawa, S. Sakka, Y. Sugahara, K. Kuroda and C. Kato, Nippon Seramikkusu Kyokai Gakujyutu Ronbunshi (J. Ceram. Soc. Jpn.), 1990, 98, 647 Search PubMed.
  27. Y. Sugahara, S. Okada, K. Kuroda and C. Kato, J. Non-Cryst. Solids, 1992, 139, 25 CAS.
  28. Y. Sugahara, S. Okada, S. Sato, K. Kuroda and C. Kato, J. Non-Cryst. Solids, 1994, 167, 21 CrossRef CAS.
  29. S. Suda, M. Iwaida, K. Yamashita and T. Umegaki, J. Non-Cryst. Solids, 1994, 176, 26 CrossRef CAS.
  30. F. Brunet, P. Lux and J. Virlet, New J. Chem., 1994, 18, 1059 Search PubMed.
  31. R. C. Chambers, W. E. Jones, Jr., Y. Haruvy, S. E. Webber and M. A. Fox, Chem. Mater., 1993, 5, 1486.
  32. T. Jermouni, M. Smaihi and N. Hovnanian, J. Mater. Chem., 1995, 5, 1203 RSC.
  33. G. D. Sorarù, G. D'Andrea, R. Campostrini and F. Babonneau, J. Mater. Chem., 1995, 5, 1363 RSC.
  34. F. Rousseau, C. Poinsignon, J. Garcia and M. Popall, Chem. Mater., 1995, 7, 828 CrossRef CAS.
  35. L. Delattre and F. Babonneau, Mater. Res. Soc. Symp. Proc., 1992, 346, 365.
  36. M. J. Bommel, T. N. M. Bernards and A. H. Boonstra, J. Non-Cryst. Solids, 1991, 128, 231 CrossRef CAS.
  37. Y. Sugahara, Y. Tanaka, S. Sato, K. Kuroda and C. Kato, Mater. Res. Soc. Symp. Proc., 1992, 271, 231.
  38. J. Kim, J. L. Plawsky, E. V. Wagenen and G. M. Korenowski, Chem. Mater., 1993, 5, 1118 CrossRef CAS.
  39. C. A. Fyfe, P. P. Aroca and Y. Zhang, Bull. Magn. Reson., 1994, 15, 195 Search PubMed.
  40. S. Prabakar, R. A. Assink, N. K. Raman and C. J. Brinker, Mater. Res. Soc. Symp. Proc., 1994, 346, 979 CAS.
  41. F. Babonneau, J. Maquet and J. Livage, Chem. Mater., 1995, 7, 1050 CrossRef CAS.
  42. Ref. 21, pp. 116–152.
  43. F. D. Osterholtz and E. R. Pohl, J. Adhesion Sci. Technol., 1992, 6, 127 Search PubMed.
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