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1. WO2012091965 - ELECTROCHEMICALLY MEDIATED ATOM TRANSFER RADICAL POLYMERIZATION

Publication Number WO/2012/091965
Publication Date 05.07.2012
International Application No. PCT/US2011/065578
International Filing Date 16.12.2011
IPC
C08F 4/40 2006.1
CCHEMISTRY; METALLURGY
08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
4Polymerisation catalysts
40Redox systems
CPC
C08F 2/38
CCHEMISTRY; METALLURGY
08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
2Processes of polymerisation
38Polymerisation using regulators, e.g. chain terminating agents ; , e.g. telomerisation
C08F 2/58
CCHEMISTRY; METALLURGY
08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
2Processes of polymerisation
58Polymerisation initiated by direct application of electric current
C08F 2438/01
CCHEMISTRY; METALLURGY
08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
2438Living radical polymerisation
01Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
C08F 4/40
CCHEMISTRY; METALLURGY
08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
4Polymerisation catalysts
40Redox systems
Applicants
  • CARNEGIE MELLON UNIVERSITY [US]/[US] (AllExceptUS)
  • MATYJASZEWSKI, Krzysztof [US]/[US] (UsOnly)
  • BORTOLAMEI, Nicola [IT]/[IT] (UsOnly)
  • MAGENAU, Andrew [US]/[US] (UsOnly)
  • GENNARO, Armando [IT]/[IT] (UsOnly)
  • ISSE, Abdirisak Ahmed [IT]/[IT] (UsOnly)
Inventors
  • MATYJASZEWSKI, Krzysztof
  • BORTOLAMEI, Nicola
  • MAGENAU, Andrew
  • GENNARO, Armando
  • ISSE, Abdirisak Ahmed
Agents
  • KENT, Joseph, L.
Priority Data
61/459,72417.12.2010US
61/574,89011.08.2011US
Publication Language English (en)
Filing Language English (EN)
Designated States
Title
(EN) ELECTROCHEMICALLY MEDIATED ATOM TRANSFER RADICAL POLYMERIZATION
(FR) POLYMÉRISATION RADICALAIRE PAR TRANSFERT D'ATOMES À MÉDIATION ÉLECTROCHIMIQUE
Abstract
(EN) Electrochemical reduction of an exemplary ATRP catalyst, CuIIBr2/Me6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form CuIBr2/Me6TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical "dials" allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization "on" and "off between dormant and active states by application of multistep intermittent potentials.
(FR) Selon l'invention, la réduction électrochimique d'un catalyseur de polymérisation radicalaire par transfert d'atomes (ATRP), donnée en exemple, de formule CuIIBr2/Me6TREN, est un procédé efficace de médiation et d'exécution d'une ATRP. Le début de polymérisation n'a lieu que sous l'effet du passage d'un courant cathodique atteint sous un potentiel réducteur pour former du CuIBr2/Me6TREN dans le milieu réactionnel. Le réglage sans précédent de la cinétique de polymérisation peut être obtenu grâce à des procédés électrochimiques, par modulation de la grandeur du potentiel appliqué, ce qui permet l'amélioration ou la décélération de la vitesse de polymérisation. Un réglage supplémentaire de la polymérisation est obtenu par des « boutons » électrochimiques qui permettent des améliorations de la vitesse de polymérisation par l'application de plus grands potentiels et par la possibilité de mettre en marche ou d'arrêter avec succès la polymérisation, passant d'états dormants à des états actifs, par l'application de potentiels intermittents en plusieurs étapes.
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