Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 50, Issue 5, Pages 936-943Publisher
WILEY
DOI: 10.1002/pola.25849
Keywords
ambient temperature; gel permeation chromatography (GPC); living radical polymerization (LRP); methyl methacrylate (MMA); reversible-deactivation radical polymerization (RDRP); single electron transfer-living radical polymerization (SET-LRP); zero-valent copper; zero-valent iron
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Funding
- National Nature Science Foundation of China [20904036, 21174094]
- Specialized Research Fund for the Doctoral Program of Higher Education [200802850005]
- Nature (Science of Higher Education of Jiangsu Province) [09KJB150010]
- Qing Lan Project
- Soochow University
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In this work, bimetallic zero-valent metal (Fe(0) powder and Cu(0) powder) was used to mediate the single electron transfer-living radical polymerization (SET-LRP) of methyl methacrylate at 25 degrees C in dimethyl sulfoxide. Different feed ratios of [Fe(0)]0/[Cu(0)]0 (0/1.5, 0.5/1, 0.75/0.75, 1/0.5, and 1.3/0.2) were explored. With the increase of Fe(0) feed, the polymerization rate was mildly depressed with a prolonged induction period. While, the control over the molecular weights was improved upon the increase of Fe(0). A best control (initiation efficiency = 91%) was achieved at [Fe(0)]0/[Cu(0)]0 = 1/0.5. A further increase of Fe(0) to the feed ratio of [Fe(0)]0:[Cu(0)]0 = 1.3: 0.2 led to a uncontrolled polymerization. Explorations of available solvents and ligands for this polymerization confirmed the SET-LRP mechanism. It was suggested that Fe(0) might act as a dual role in this process: one was the activation agent for Cu(0), which favored a better control over the molecular weights; The other was an alternative catalyst for the activation of R-X or Pn-X to generate radicals, which assured a comparable polymerization rate as that of Cu(0). This work provided an alternative and economical catalyst for SET-LRP, and would eventually reinforce the SET-LRP technique. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
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