Atom Transfer Radical Copolymerization of α ‐Olefins with Methyl Acrylate: Determination of Activation Rate Parameters

Summary: The activation rate parameters of three model compounds for an acrylate/ α ‐olefin atom transfer radical copolymerization were investigated. It appeared that the activation of the model compound for the dormant acrylate chain (methyl‐2‐bromopropionate) was quite fast ( k act  = 0.018 (±0.001) L · mol −1  · s −1 at 0 °C). The activation of the model compound for the dormant α ‐olefin chain end (2‐bromobutane) did not take place at any appreciable rate (0 and 35 °C). The introduction of a penultimate acrylate unit in the model compound for the dormant α ‐olefin chain end (H‐MA‐hexene‐Br) did not result in any activation at 0 and 35 °C. Only at 70 °C some activation was visible after 18 h reaction time. By inference, these results confirm our earlier conclusion that the ATR copolymerization of acrylates and α ‐olefins is possible due to the fast crosspropagation of an α ‐olefin chain end radical with an acrylate.1 H NMR spectra for the MBrP/Cu(I)Br/PMDETA/hydroxy TEMPO (1/10/10/10) mixture.