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Title: Synthesis of star and H-shape polymers via a combination of cobalt-mediated radical polymerization and nitrone-mediated radical coupling reactions
Authors: Detrembleur, Christophe
Debuigne, Antoine
Altintas, Ozcan
CONRADI, Matthias Horst 
Wong, Edgar H. H.
Jerome, Christine
Barner-Kowollik, Christopher
Issue Date: 2012
Source: POLYMER CHEMISTRY, 3(1), p. 135-147
Abstract: Via consecutive cobalt-mediated radical polymerization (CMRP), nitrone-mediated radical coupling (NMRC) and copper catalyzed azide-alkyne cycloaddition (CuAAC), polymers with mikto-arm star and H-shape architecture were synthesized. Poly(vinyl acetate)(40)-block-poly(acrylonitrile)(78)-Co(acac)(2) polymers were synthesized via CMRC and subsequently coupled using an alkyne functional nitrone. The coupling efficiency of the NMRC process was assessed employing N-tert-butyl alpha-phenyl nitrone (PBN), which is structurally very similar to the later employed coupling agent. Generally, coupling efficiencies of close to 90% or higher were observed in all cases. Since the coupling reaction yields triblock copolymers bearing an alkoxyamine functionality (and thus also an alkyne group) in the middle of the chain, well defined PEG conjugates could be obtained via CuAAC. Miktoarm star polymers of the structure (PVAc-b-PAN)(2)-PEG were generated as well as H-shaped material of the structure (PVAc-b-PAN)(2)-PEG-(PVAc-b-PAN)(2) via conjugation with bifunctional PEG. In all cases, very narrow molecular weight material was obtained. Molecular weight analysis of the intermediate and the final products reveals that the hydrodynamic volume of the miktoarm star and the H-shaped materials is not substantially increased during the final conjugation reaction despite the fact that the absolute molecular weight increases by more than a factor of two in the latter case. Success of the conjugation reactions was confirmed via composition analysis via NMR.
Notes: [Detrembleur, Christophe; Debuigne, Antoine; Jerome, Christine] Univ Liege, CERM, B-4000 Liege, Belgium. [Altintas, Ozcan; Wong, Edgar H. H.; Barner-Kowollik, Christopher] KIT, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany. [Conradi, Matthias; Junkers, Thomas] Univ Hasselt, Inst Mat Res IMO, Polymer React Design Grp, BE-3590 Diepenbeek, Belgium.
Keywords: Polymer Science; spin capturing; polymerization; molecular-weight distributions; click chemistry; block-copolymers; vinyl acetate; styrene; cycloaddition; conjugation; efficient; kinetics
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ISSN: 1759-9954
e-ISSN: 1759-9962
DOI: 10.1039/c1py00297j
ISI #: 000298547200015
Category: A1
Type: Journal Contribution
Validations: ecoom 2013
Appears in Collections:Research publications

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