Polymer Bulletin

, Volume 35, Issue 3, pp 245–250 | Cite as

Novel polymerization of divinyl monomer to polyester catalyzed with organocobaloxime

  • Bunichiro Yamada
  • Kenji Toda
  • Shuzo Aoki


The polymerization of ethylene bis(α-ethylacrylate) to polyester was catalyzed with benzyl(bisdimethylglyoximato)(pyridine)cobalt(III). Although the α-ethylacrylic ester does not radically homopolymerize, radical addition to the carbon-carbon double bond yields the corresponding radical. This radical readily reacts with the cobalt(II) complex involved to form a carbon-cobalt bond. Dissociation of the generated bond accompanying fast β-hydrogen elimination results in a new carbon-carbon double bond and the cobalt hydride which rapidly adds to the ethylacrylate moiety to form a carbon radical which may react with the cobalt(II) complex. Through the sequence of these reactions, the novel polyester linkage was expected to be formed. Actually, the cobaloxime catalyzed reaction competed with radical propagation, and the polymer consisted of the polyester linkage (32%) and the consecutive ethylacrylate units with two types of unsaturated pendant groups (68%).


Ester Cobalt Pyridine Hydride Benzyl 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Enikolopyan NS, Smirnov BR, Ponomarev GV, Belgovskii IM (1981)J Polym Sci: Part A: Polym Chem 19: 879Google Scholar
  2. 2.
    Burczyk AC, O'Driscoll KF, Rempel GC (1984)J Polym Sci: Part A: Polym Chem 27: 3255Google Scholar
  3. 3.
    Gridnev AA (1992)Polym J 24: 613Google Scholar
  4. 4.
    Gridnev AA, Ittel SD, Fryd M, Wayland BB (1993)J Chem Soc Chem Commun 1010Google Scholar
  5. 5.
    Davis TP, Haddleton DM, S. N. Richards SN (1994)J Macromol Sci Rev, Macromol Chem Phys C34: 274Google Scholar
  6. 6.
    Cacioli P, Hawthorne DG, Laslett RC, Rizzardo E, Solomon DH (1986)J Macromol Sci Chem A23: 839Google Scholar
  7. 7.
    Yamada B, Tagashira S, Aoki S (1994)J Polym Sci: Part A: Polym Chem 32: 2745Google Scholar
  8. 8.
    Giese B “Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds” Pergamon Press, Oxford, 1986.Google Scholar
  9. 9.
    Odian G “Principles of Polymerization”, 3rd Ed., Wiley, 1991, p. 438Google Scholar
  10. 10.
    Saegusa T, Kobayashi S, Kimura Y (1974)Macromolecules 7: 256Google Scholar
  11. 11.
    Yamada B, Yasuda Y, Matsushita T, Otsu T (1976)J Polym Sci, Polym Lett Ed 14: 277; (1978)Kobunshi Ronbunshyu 35: 607Google Scholar
  12. 12.
    Takada T, Endo T (1993)Prog Polym Sci 18: 839Google Scholar
  13. 13.
    p. 517 of ref 9Google Scholar
  14. 14.
    Johnson MD (1983)Acc Chem Res 16: 343Google Scholar
  15. 15.
    Tsun YT, Loots M, Halpern J (1982)J Am Chem Soc 104: 623Google Scholar
  16. 16.
    Penelle J, Collot J, Rufflard G (1993)J Polym Sci: Part A: Polym Chem 31: 2407Google Scholar

Copyright information

© Springer-Verlag 1995

Authors and Affiliations

  • Bunichiro Yamada
    • 1
  • Kenji Toda
    • 1
  • Shuzo Aoki
    • 1
  1. 1.Material Chemistry Laboratory and Department of Applied Chemistry, Faculty of EngineeringOsaka City UniversityOsakaJapan

Personalised recommendations