Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum

  • 86 Accesses

  • 39 Citations

Summary

Polymerization of methyl methacrylate (MMA) withtert-butyllithium (t-C4H9Li) in toluene in the presence of aluminum alkoxides such as ethoxide,tert-butoxide and 2,6-di-tert-butylphenoxide, were examined at various Al/Li ratios. In the cases of ethoxide andtert-butoxide, predominantly isotactic polymers with broad molecular weight distribution were obtained. Combinations oft-C4H9Li and bis(2,6-ditert-butylphenoxy)methylaluminum [MeAl(ODBP)2] were found to be an efficient initiating system for heterotactic polymerization of MMA, which gives PMMA rich in heterotactic triads up to 68% with narrow molecular weight distribution (Mw/Mn=1.09−1.17). End group analysis by1H NMR indicated thatt-C4H9Li initiates the polymerization and MeAl(ODBP)2 works as a stereospecific modifier. From stereosequence analysis of the heterotactic PMMA by13C NMR, it was found that the calculated pentad fractions from the first-order Markovian statistics (Pm/r=0.742, Pr/m=0.627) fitted the observed ones better than those from Bernoullian statistics. The glass transition temperature of the heterotactic PMMA was 13°C lower than that of syndiotactic PMMA, and the intrinsic viscosity in tetrahydrofuran was close to that of isotactic PMMA with a similar molecular weight but higher than that of syndiotactic PMMA.

This is a preview of subscription content, log in to check access.

References

  1. 1.

    H. Yuki and K. Hatada,Adv. Polym. Sci.,31, 1 (1979).

  2. 2.

    K. Hatada, T. Kitayama, and K. Ute,Prog. Polym. Sci.,13, 189 (1989).

  3. 3.

    K. Hatada, H. Sugino, H. Ise, T. Kitayama, Y. Okamoto, and H. Yuki,Polym. J.,12, 55 (1980).

  4. 4.

    S. Nozakura, T. Okamoto, K. Toyora, and S. Murahashi,J. Polym. Sci., Polym. Chem. Ed.,11, 1043 (1973).

  5. 5.

    S. Nozakura, S. Ishihara, Y. Inaba, K. Matsumura, and S. Murahashi,J. Polym. Sci., Polym. Chem. Ed.,11, 1053 (1973).

  6. 6.

    E. G. Brame, Jr. and O. Vogl,J. Macromol. Sci, Chem. A1, 277 (1967).

  7. 7.

    M. Goodman and J. Brandrup,J. Polym. Sci.,A3, 327 (1965).

  8. 8.

    M. Reinmoller and T. G. Fox,Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem.,7, 999 (1966).

  9. 9.

    W. T. Gibbs and J. T. Murray,J. Polym. Sci.,58, 141 (1962).

  10. 10.

    J. C. H. Hwa,J. Polym. Sci.,60, S12 (1962).

  11. 11.

    G. Smets, P. Hous, and N. Deval,J. Polym. Sci.,A2, 4825 (1964).

  12. 12.

    M. Reinmoller and T. G. Fox,Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem.,7, 1005 (1966).

  13. 13.

    M. Kammerer,Weyerhaeuser Sci. Symp. Volume Data 1979,2 (Phenolic Resins: Chem. Appl.), 17 (1980).

  14. 14.

    K. Hatada, T. Kitayama, T. Ochi, and H. Yuki,Polym. J.,19, 1005 (1987).

  15. 15.a)

    Y. Gotoh, T. Iihara, N. Kanai, N. Toshima and H. Hirai,Chem. Lett., 2157 (1990)

  16. 15.b)

    Y. Gotoh, M. Yamashita, M. Nakamura, N. Toshima, and H. Hirai,Chem. Lett., 53 (1991).

  17. 16.

    T. Kitayama, T. Shinozaki, E. Masuda, M. Yamamoto, and K. Hatada,Polym. Bull. 20, 505 (1988).

  18. 17.

    T. Kitayama, T. Shinozaki, T. Sakamoto, M. Yamamoto, and K. Hatada,Makromol. Chem., Supplement. 15, 167 (1989).

  19. 18.

    T. Kitayama, E. Masuda, M. Yamaguchi, T. Nishiura, and K. Hatada,Polym. J.,24, 817 (1992).

  20. 19.

    S. Murahashi, T. Niki, T. Obokata, H. Yuki, and K. Hatada,Kobunshi Kagaku,24, 198 (1967).

  21. 20.

    S. Murahashi, T. Obokata, H. Yuki and, K. Hatada,Kobunshi Kagaku,24, 309 (1967).

  22. 21.

    S. C. Watson and J. F. Eastham,J. Organomet. Chem.,9, 165 (1965).

  23. 22.

    K. Maruoka and H. Yamamoto,Angew. Chem., Int. Ed. Engl.,24, 668 (1985).

  24. 23.

    K. Maruoka, T. Itoh, M. Sakura, K. Nonoshita, and H. Yamamoto,J. Am. Chem. Soc.,110, 3588 (1988).

  25. 24.

    M. Kuroki, T. Watanabe, T. Aida, and S. Inoue,J. Am. Chem. Soc.,113, 5903 (1991).

  26. 25.

    T. Adachi, H. Sugimoto, T. Aida, and S. Inoue,Macromolecules,25, 2280 (1992).

  27. 26.

    H. Sugimoto, M. Kuroki, T. Watanabe, C. Kawamura, T. Aida, and S. Inoue,Macromolecules,26, 3403 (1993).

  28. 27.

    D. G. H. Ballard, R. J. Bowles, D. M. Haddleton, S. N. Richards, R. Sellens, and D. L. Twose,Macromolecules,25, 5907 (1992).

  29. 28.

    M. Miyamoto, N. Miwa, and K. Hasegawa,Polym. Prep. Jpn. 40, 1855 (1991).

  30. 29.a)

    M. D. Healy, D. A. Wierda, and A. R. Barron,Organometallics,7, 2543 (1988)

  31. 29.b)

    M. D. Healy, J. W. Ziller, and A. R. Barron,J. Am. Chem. Soc.,112, 2949 (1990).

  32. 30.a)

    M. Skowronska-Ptasinska, K. B. Starowieyski, S. Pasynkiewicz, and M. Carewska,J. Organomet. Chem.,160, 403 (1978)

  33. 30.b)

    A. P. Streve, R. Mulhaupt, W. Fultz, J. Calabrese, W. Robbins, and S. D. Ittel,Organometallics,7, 409 (1988)

  34. 30.c)

    R. Benn, E. Janssen, H. Lehmkuhl, A. Rufinska, K. Augermund, P. Betz, R. Goddard, and C. Kruger,J. Organomet. Chem.,411, 37 (1991).

  35. 31.

    M. D. Healy and A. R. Barron,Angew. Chem. Int. Ed. Engl. 31, 921 (1992).

  36. 32.

    T. Kitayama, Y. J. Zhang, and K. Hatada,to be submitted to Polym. J.

Download references

Author information

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Kitayama, T., Zhang, Y. & Hatada, K. Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum. Polymer Bulletin 32, 439–446 (1994). https://doi.org/10.1007/BF00587886

Download citation

Keywords

  • PMMA
  • Glass Transition Temperature
  • Alkoxide
  • Molecular Weight Distribution
  • Methyl Methacrylate