Atom transfer radical copolymerization of α-olefins with methyl acrylate: determination of activation rate parameters

The activation rate parameters of three model compds. for an acrylate/a-olefin atom transfer radical copolymn. were investigated. It appeared that the activation of the model compd. for the dormant acrylate chain (methyl-2-bromopropionate) was quite fast (kact=0.018 (+-0.001) L.mol-1.s-1 at 0 DegC). The activation of the model compd. for the dormant a-olefin chain end (2-bromobutane) did not take place at any appreciable rate (0 and 35 DegC). The introduction of a penultimate acrylate unit in the model compd. for the dormant a-olefin chain end (H-MA-hexene-Br) did not result in any activation at 0 and 35 DegC.Only at 70 DegC some activation was visible after 18 h reaction time. By inference, these results confirm our earlier conclusion that the ATR copolymn. of acrylates and a-olefins is possible due to the fast crosspropagation of an a-olefin chain end radical with an acrylate