Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 47, Issue 21, Pages 5591-5605Publisher
WILEY
DOI: 10.1002/pola.23689
Keywords
kinetics; living polymerization; methyl acrylate; radical polymerization; SET-LRP
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Funding
- National Science Foundation [DMR-0548559, DMR-0520020]
- National Science Foundation Graduate Research Fellowship
- American Chemical Society Division of Organic Chemistry Graduate Fellowship (Sponsored by Roche, Inc.)
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SET-LRP requires a combination of ligand and solvent that mediates the disproportionation of Cu(I)X into Cu(O) activator, and Cu(II) deactivator. The solvent also modulates the kinetics of the reaction. More polar solvents, including mixtures of water and organic solvents enhance the rate of polymerization in accord with the Dimroth-Reichardt parameter. Here, it is demonstrated that a similar effect is observed in binary mixtures of organic solvents, wherein the addition of a more polar solvent to a less polar solvent provides a linear increase in the apparent rate constant of propagation, k(p)(app). However, this linear relationship does not hold for the entire range of volume fraction for binary mixtures when ethylene carbonate (EC) or MeOH are one of the two components. Results herein, suggest that the kinetics of SET-LRP in these solvent mixtures is cooperatively and synergistically determined by polarity, degree of disproportionation, and also by another parameter related to the ability of the solvent to stabilize colloidal Cu(O) and determine its particle size. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5591-5605, 2009
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