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Effect of the Ligand in Atom Transfer Radical Polymerization Reactions Initiated by Photodimers of 9-Bromoanthracene

  1. Nicole A. Cohen1,
  2. Eric S. Tillman1,*,
  3. Sona Thakur1,
  4. Jenell R. Smith1,
  5. William T. Eckenhoff2,
  6. Tomislav Pintauer2

Article first published online: 30 DEC 2008

DOI: 10.1002/macp.200800481

Issue

Macromolecular Chemistry and Physics

Macromolecular Chemistry and Physics

Volume 210, Issue 3-4, pages 263–268, February 20, 2009

Additional Information

How to Cite

Cohen, N. A., Tillman, E. S., Thakur, S., Smith, J. R., Eckenhoff, W. T. and Pintauer, T. (2009), Effect of the Ligand in Atom Transfer Radical Polymerization Reactions Initiated by Photodimers of 9-Bromoanthracene. Macromol. Chem. Phys., 210: 263–268. doi: 10.1002/macp.200800481

Author Information

  1. 1

    Department of Chemistry, Bucknell University, Lewisburg, Pennsylvania 17837, USA

  2. 2

    Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, USA

*Department of Chemistry, Bucknell University, Lewisburg, Pennsylvania 17837, USA.

Publication History

  1. Issue published online: 10 FEB 2009
  2. Article first published online: 30 DEC 2008
  3. Manuscript Accepted: 20 NOV 2008
  4. Manuscript Revised: 18 NOV 2008
  5. Manuscript Received: 29 SEP 2008

Funded by

  • Research Corporation. Grant Number: CC6284
  • Bucknell University Program

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Keywords:

  • atom transfer radical polymerization (ATRP);
  • gel permeation chromatography (GPC);
  • polystyrene

Abstract

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Slow initiation from the bridgehead radical in atom transfer radical polymerization (ATRP) reactions initiated by 9-bromoanthracene photodimers leads to polymers' products possessing high PDI values and higher than expected equation image values. We report here the effects of changing the ligand from N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) to the highly active tris[2-(dimethylamino)ethyl]amine (Me6TREN) or tris[(2-pyridyl)methyl]amine (TPMA) in an attempt to push the initial equilibrium further toward the initiating bridgehead radical. Overall, the ligand choice was found to add negligible control to the ATRP of styrene with any increase in the rate of initiation offset by an increase in the rate of propagation, leading to anthracene-labeled polystyrene with similar PDI (≈1.6) and equation image values regardless of the ligand choice.

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