Journal
MACROMOLECULES
Volume 42, Issue 7, Pages 2379-2386Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma8028562
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Funding
- National Science Foundation [DMR-0548559, DMR-0520020]
- NSF Graduate Research Fellowship
- ACS Division of Organic Chemistry Graduate Fellowship
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The effect of Cu(0) wire dimensions Oil the Cu(0) wire/Me-6-TREN-catalyzed heterogeneous single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA) initiated with methyl 2-bromopropionate (MBP) in DMSO at 25 degrees C was analyzed by kinetic experiments. These kinetic results were compared with those of Cu(0) powder/Me-6-TREN-catalyzed SET-LRP. Both wire and powder produce perfect SET-LRP with a first-order rate of polymerization in growing species Lip to 100% conversion. Nevertheless, Cu(0) wire experiments demonstrated SET-LRP with greater perfection, allowing for the accurate determination of the external rate order (vis-a-vis Surface area) for heterogeneous Cu(0) catalyst and accurate prediction of k(p)(app) from wire dimension. Cu(0) wire also exhibited a significantly greater control of molecular weight distribution than Cu(0) powder. The combined advantages of easier catalyst preparation, handling, predictability, tunability, simple recovery/recycling, and enhanced control of molecular weight distribution make Cu(0)-wire-catalyzed SET-LRP the ideal methodology for the synthesis of tailored polyacrylates.
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