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

✍ Scribed by Rajan Venkatesh; Frank Vergouwen; Bert Klumperman

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 328 KB
• Volume: 206
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.200400389

✦ Synopsis

Abstract

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.

magnified image^1^H NMR spectra for the MBrP/Cu(I)Br/PMDETA/hydroxy TEMPO (1/10/10/10) mixture.