Pressure Dependence of Iron‐Mediated Methyl Methacrylate ATRP in Different Solvent Environments
Identifieur interne : 004746 ( Main/Exploration ); précédent : 004745; suivant : 004747Pressure 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.
Descripteurs français
- Pascal (Inist)
- Activation, Activation désactivation, Brome Composé organique, Cinétique chimique, Complexe de fer, Constante équilibre, Effet pression, Effet solvant, Etude expérimentale, Méthacrylate de méthyle polymère, Polymère vivant, Polymérisation solution, Polymérisation sous pression, Polymérisation transfert atome, Réaction réversible.
English descriptors
- KwdEn :
- Activation, Atom transfer polymerization, Bromine Organic compounds, Chemical reaction kinetics, Equilibrium constant, Experimental study, Iron complex, Living polymer, Methyl methacrylate polymer, Polymerization under pressure, Pressure effect, Reversible reaction, Solution polymerization, Solvent effect.
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.
Url:
DOI: 10.1002/macp.201300505
Affiliations:
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Buback</name><affiliation wicri:level="3"><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institute of Physical Chemistry, Georg‐August‐University, Tammannstrasse 6, Goettingen, 37077</wicri:regionArea><placeName><region type="land" nuts="2">Basse-Saxe</region><settlement type="city">Göttingen</settlement></placeName></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Allemagne</country></affiliation></author><author><name sortKey="Matyjaszewski, Krzysztof" sort="Matyjaszewski, Krzysztof" uniqKey="Matyjaszewski K" first="Krzysztof" last="Matyjaszewski">Krzysztof Matyjaszewski</name><affiliation wicri:level="4"><country xml:lang="fr">États-Unis</country><wicri:regionArea>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, PA, 15213, Pittsburgh</wicri:regionArea><placeName><settlement type="city">Pittsburgh</settlement><region type="state">Pennsylvanie</region><settlement type="city">Pittsburgh</settlement></placeName><orgName type="university">Université Carnegie-Mellon</orgName></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Macromolecular Chemistry and Physics</title><title level="j" type="alt">MACROMOLECULAR CHEMISTRY AND PHYSICS</title><idno type="ISSN">1022-1352</idno><idno type="eISSN">1521-3935</idno><imprint><biblScope unit="vol">215</biblScope><biblScope unit="issue">1</biblScope><biblScope unit="page" from="44">44</biblScope><biblScope unit="page" to="53">53</biblScope><biblScope unit="page-count">10</biblScope><date type="published" when="2014-01">2014-01</date></imprint><idno type="ISSN">1022-1352</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1022-1352</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Activation</term><term>Atom transfer polymerization</term><term>Bromine Organic compounds</term><term>Chemical reaction kinetics</term><term>Equilibrium constant</term><term>Experimental study</term><term>Iron complex</term><term>Living polymer</term><term>Methyl methacrylate polymer</term><term>Polymerization under pressure</term><term>Pressure effect</term><term>Reversible reaction</term><term>Solution polymerization</term><term>Solvent effect</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Activation</term><term>Activation désactivation</term><term>Brome Composé organique</term><term>Cinétique chimique</term><term>Complexe de fer</term><term>Constante équilibre</term><term>Effet pression</term><term>Effet solvant</term><term>Etude expérimentale</term><term>Méthacrylate de méthyle polymère</term><term>Polymère vivant</term><term>Polymérisation solution</term><term>Polymérisation sous pression</term><term>Polymérisation transfert atome</term><term>Réaction réversible</term></keywords></textClass></profileDesc></teiHeader><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></front></TEI><affiliations><list><country><li>Allemagne</li><li>États-Unis</li></country><region><li>Basse-Saxe</li><li>Pennsylvanie</li></region><settlement><li>Göttingen</li><li>Pittsburgh</li></settlement><orgName><li>Université Carnegie-Mellon</li></orgName></list><tree><country name="Allemagne"><region name="Basse-Saxe"><name sortKey="Schroeder, Hendrik" sort="Schroeder, Hendrik" uniqKey="Schroeder H" first="Hendrik" last="Schroeder">Hendrik Schroeder</name></region><name sortKey="Buback, Michael" sort="Buback, Michael" uniqKey="Buback M" first="Michael" last="Buback">Michael Buback</name><name sortKey="Buback, Michael" sort="Buback, Michael" uniqKey="Buback M" first="Michael" last="Buback">Michael Buback</name></country><country name="États-Unis"><region name="Pennsylvanie"><name sortKey="Matyjaszewski, Krzysztof" sort="Matyjaszewski, Krzysztof" uniqKey="Matyjaszewski K" first="Krzysztof" last="Matyjaszewski">Krzysztof Matyjaszewski</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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