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Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence
Ist Teil von
Angewandte Chemie (International ed.), 2017-01, Vol.56 (2), p.519-523
Auflage
International ed. in English
Ort / Verlag
Germany: Wiley Subscription Services, Inc
Erscheinungsjahr
2017
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible‐light irradiation of dimanganese decacarbonyl (Mn2(CO)10) in the presence of an alkyl bromide results in the formation of carbon‐centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then rapidly deactivated by the bromide anions to give α‐halide functional end groups. Poly(vinyl ether) chains are then grown through successive photoinduced radical oxidation/addition/deactivation (PROAD) in a controlled manner. The living nature of the system is evaluated through kinetics studies and block copolymer formation.
The living daylights: A photoinitiation approach was developed for living cationic polymerization of vinyl ethers by using Mn2(CO)10 in the presence of alkyl halide and oxidant under visible‐light irradiation. The living nature of the polymerization was demonstrated through investigation of time dependence of logarithmic conversion and molecular weight. The potential of the system for the synthesis of block copolymers was also demonstrated.