Study on the Polymerization Characteristics of Isoprene through Nitroxide Mediated Controlled/"living" Radical Polymerization Techniques

Nitroxide 매개 리빙라디칼 중합법에 의한 isoprene의 중합특성에 관한 연구

  • Hong, Sung-Chul (Department of Nano Science and Technology, Sejong University)
  • Published : 2009.03.30


In this study, investigation on the polymerization characteristics of isoprene through nitroxide mediated controlled/"living" radical polymerization techniques was attempted. In the presence of acetol, linear increase of isoprene conversion with time and low polydispersities of the resulting polymers ($M_w/M_n$ < 1.5) were observed, which suggest successful controlled/"living" radical polymerization of isoprene. The microstructure of the resulting polyisoprene was composed of $\sim$ 22% of 3, 4, $\sim$30% of 1, 4-cis and $\sim$ 48% of 1, 4-trans. The optimum polymerization temperature was 145 $^{circ}C$, below which no significant polymerization behavior was observed. Non-cyclic nitroxide, such as di-tert-butyl nitroxide (DTBN) could not mediate the polymerization, whereas cyclic nitroxides (2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (TEMPO) and 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (oxoTEMPO)) were successfully employed for the polymerization. However, isoprene dimerization reaction through Diels-Alder process was also observed at the given polymerization condition, which afforded a significant amount of limonene. Isoprene thermal autoinitiation was also possible, which was, however, considered to be not significant under the given polymerization condition.


  1. M. Fontanille and Y. Gnanou, 'Anionic Polymerization of Vinyl and Related Monomers'. In Macromolecular Engineering, ed. by K. Matyjaszewski, Y. Gnanou and L. Leibler, 1st ed., p. 7, Wiley-VCH Verlag GmbH, Weinheim, 2007
  2. W. A. Braunecker and K. Matyjaszewski, 'Controlled/living radical polymerization: Features, developments, and perspectives', Prog. Polym. Sci., 32, 93 (2007)
  3. K. Matyjaszewski, 'Macromolecular engineering: From rational design through precise macromolecular synthesis and processing to targeted macroscopic material properties', Prog. Polym. Sci., 30, 858 (2005)
  4. N. Hadjichristidisa, H. Iatroua, M. Pitsikalisa, and J. Mays, 'Macromolecular architectures by living and controlled/living polymerizations', Prog. Polym. Sci., 31, 1068 (2006)
  5. M. K. Georges, R. P. N. Veregin, P. M. Kazmaier, and G. K. Hamer, 'Narrow molecular weight resins by a free-radical polymerization process', Macromolecules, 26, 2987 (1993)
  6. C. J. Hawker, A. W. Bosman, and E. Harth, 'New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations', Chem. Rev., 101, 3661 (2001)
  7. K. Matyjaszewski and J. Xia, 'Atom Transfer Radical Polymerization', Chem. Rev., 101, 2921 (2001)
  8. M. Kamigaito, T. Ando, and M. Sawamoto, 'Metal- Catalyzed Living Radical Polymerization', Chem. Rev., 101, 3689 (2001)
  9. J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, and S. H. Thang, 'Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer: The RAFT Process', Macromolecules, 31, 5559 (1998)
  10. J. Wootthikanokkhan, M. Peesan and P. Phinyocheep, 'Atom transfer radical polymerizations of (meth)acrylic monomers and isoprene', Eur. Polym. J., 37, 2063 (2001)
  11. V. Jitchum and S. b. Perrier, 'Living Radical Polymerization of Isoprene via the RAFT Process', Macromolecules, 40, 1408 (2007)
  12. B. Keoshkerian, M. Georges, M. Quinlan, R. Veregin, and B. Goodbrand, 'Polyacrylates and Polydienes to High Conversion by a Stable Free Radical Polymerization Process: Use of Reducing Agents', Macromolecules, 31, 7559 (1998)
  13. D. Benoit, E. Harth, P. Fox, R. M. Waymouth, and C. J. Hawker, 'Accurate Structural Control and Block Formation in the Living Polymerization of 1,3-Dienes by Nitroxide-Mediated Procedures', Macromolecules, 33, 363 (2000)
  14. J. K. Wegrzyn, T. Stephan, R. Lau, and R. B. Grubbs, 'Preparation of Poly(ethylene oxide)-block- poly(isoprene) by Nitroxide-Mediated Free Radical Polymerization from PEO Macroinitiators', J. Polym. Sci., Part A: Polym. Chem., 43, 2977 (2005)
  15. R. B. Grubbs, J. M. Dean, M. E. Broz, and F. S. Bates, 'Reactive Block Copolymers for Modification of Thermosetting Epoxy', Macromolecules, 33, 9522 (2000)
  16. M. K. Georges, G. K. Hamer, and N. A. Listigovers, 'Block Copolymer Synthesis by a Nitroxide- Mediated Living Free Radical Polymerization Process', Macromolecules, 31, 9087 (1998)
  17. H. Sato and Y. Tanaka, '1H-NMR study of polyisoprenes', J. Polym. Sci., Part A: Polym. Chem., 17, 3551 (1979)