Polymer Bulletin

, Volume 58, Issue 5–6, pp 881–891 | Cite as

Photodimers of 9-Haloanthracenes as Initiators in Atom Transfer Radical Polymerization: Effect of the Bridgehead Halogen

  • Eric S. Tillman
  • Daniel J. Miller
  • Amanda C. Roof


Photodimers of 9-chloroanthracene, formed by a [4+4] cycloaddition reaction of 9-chloroanthracene, were used as initiators in the atom transfer radical polymerization of styrene and compared to results previously obtained using photodimers of 9-bromoanthracene as the initiator. Heat-induced cleavage of the photodimer coupled with slow initiation from the bridgehead radical have been used to account for the lack of control in the systems, and thus changing the halogen on the initiating photodimer could support or refute this model. Reactions performed using analogous procedures produced polymers with number average molecular weight (Mn) values significantly higher in the case of 9-chloroanthracene photodimer-initiated systems, with similar polydispersity index (PDI) values observed in trials catalyzed with CuCl or CuBr. Polymer products showed absorbance bands indicative of regenerated anthracene in all cases, consistent with heat-induced cleavage of the photodimer during the course of the polymerization. Kinetic plots demonstrated that the polymerizations initiated with photodimers of 9-chloroanthracene showed maximum Mn values were obtained after approximately 10% monomer conversion, with a decline in Mn as a function of monomer conversion after this point. The data support slower initiation in the case of 9-chloroanthracene photodimers, followed by heat-induced cleavage throughout the polymerization system.


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References and Notes

  1. 1.
    Nanda AK, Matyjaszewski K (2003) Macromolecules 36:599.Google Scholar
  2. 2.
    Gromada J, Matyjaszewski K (2001) Macromolecules 34:7664.Google Scholar
  3. 3.
    Zhang X, Matyjaszewski K (1999) Macromolecules 32:7349.Google Scholar
  4. 4.
    Tong JD, Ni S, Winnik MA (2000) Macromolecules 33:1482.Google Scholar
  5. 5.
    Wang G, Zhu X, Zhenping C, Zhu JJ (2005) J Polym Sci Part A, Polym Chem 43:2358.Google Scholar
  6. 6.
    Goodman CC, Roof AC, Tillman ES, Ludwig B, Chon D, Weigley MI (2005) J Polym Sci Part A, Polym Chem 43:2657.Google Scholar
  7. 7.
    Braunecker WA, Itami Y, Matyjaszewski K (2005) Macromolecules 38:9402.Google Scholar
  8. 8.
    Roof AC, Tillman ES, Malik RE, Roland AM, Miller DJ, Sarry LR (2006) Polymer 47:3325.Google Scholar
  9. 9.
    Pokorna V, Vyprachticky D, Pecka J, Mikes FJ (1999) J Fluoresc 9:59.Google Scholar
  10. 10.
    Bouas-Laurent H, Castellan A, Desvergne JP, Lapouyad R (2000) Chem Soc Rev 29:43.Google Scholar
  11. 11.
    Breton GW, Vang XJ (1998) J Chem Educ 75:81.Google Scholar
  12. 12.
    Ito Y, Fujito HJ (1996) Org Chem 61:5677.Google Scholar
  13. 13.
    Applequist DE, Searle R, Steinhardt MD, Friedrich EC, Little LJ (1965) Org Chem 30:2126.Google Scholar
  14. 14.
    Shipp DA, Wang J-L, Matyjaszewski (1998) K. Macromolecules 31:8005.Google Scholar
  15. 15.
    Cheng Z, Zhu X, Kang ET, Neoh KG (39) Macromolecules 39:1660.Google Scholar
  16. 16.
    Wang JS, Matyjaszewski K (1995) Am Chem Soc 117:5614.Google Scholar
  17. 17.
    Wang JS, Matyjaszewski K (1995) Macromolecules. 26:7901.Google Scholar
  18. 18.
    Pangborn AB, Giardello MA, Grubbs RH, Rosen RK Timmers FJ (1996) Organometallics 15:1518.Google Scholar
  19. 19.
    ε=10000 cm-1M-1 near 370 nm for anthracene. Anthracene content was calculated using Beer-Lambert’s law.Google Scholar
  20. 20.
    Matyjaszewski K, Shipp DA, Wang JS, Grimaud T, Patton TE (1998) Macromolecules 31:6836.Google Scholar

Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  • Eric S. Tillman
    • 1
  • Daniel J. Miller
    • 1
  • Amanda C. Roof
    • 1
  1. 1.Department of ChemistryBucknell UniversityLewisburg

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