Pressure Dependence of Iron‐Mediated Methyl Methacrylate ATRP in Different Solvent Environments
Identifieur interne : 004978 ( Main/Merge ); précédent : 004977; suivant : 004979Pressure Dependence of Iron‐Mediated Methyl Methacrylate ATRP in Different Solvent Environments
Auteurs : Hendrik Schroeder [Allemagne] ; Michael Buback [Allemagne] ; Krzysztof Matyjaszewski [États-Unis]Source :
- Macromolecular Chemistry and Physics [ 1022-1352 ] ; 2014-01.
Abstract
Iron‐mediated atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in N‐methylpyrrolidin‐2‐one (NMP) solution is investigated via online VIS/NIR spectroscopy up to 2500 bar. The activation–deactivation equilibrium constant, KATRP, decreases towards higher NMP content due to the formation of catalytically less active FeII/NMP species. The reaction volume increases from 1 to 15 cm3 mol−1 in passing from 16 to 92 mol% NMP. The same effects are observed for monomer‐free model systems with poly(MMA)–Br as the initiator. Investigations into iron‐catalyzed ATRP of MMA in less polar solvents or even without an additional solvent (i.e., for bulk ATRP) yield KATRP values, which are by two to three orders of magnitude higher than in the presence of NMP.
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DOI: 10.1002/macp.201300505
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<front><div type="abstract" xml:lang="en">Iron‐mediated atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in N‐methylpyrrolidin‐2‐one (NMP) solution is investigated via online VIS/NIR spectroscopy up to 2500 bar. The activation–deactivation equilibrium constant, KATRP, decreases towards higher NMP content due to the formation of catalytically less active FeII/NMP species. The reaction volume increases from 1 to 15 cm3 mol−1 in passing from 16 to 92 mol% NMP. The same effects are observed for monomer‐free model systems with poly(MMA)–Br as the initiator. Investigations into iron‐catalyzed ATRP of MMA in less polar solvents or even without an additional solvent (i.e., for bulk ATRP) yield KATRP values, which are by two to three orders of magnitude higher than in the presence of NMP.</div>
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