The behaviour of the 1-phenylethyl radical as an initiating species wa
s investigated using the end group method of Bevington et al. for a nu
mber of copolymerisations of methyl methacrylate with maleic anhydride
and similar species. A strong selectivity for addition of the 1,2 dis
ubstituted monomer was found in each case. The reactivity ratios obtai
ned for addition of the 1-phenylethyl radical to styrene and maleic an
hydride, when compared with published equivalents for the poly(styrene
) radical, showed addition to the 1-phenylethyl radical to be more sel
ective by a factor of approximately two. Similar results were found fo
r each of the other species examined and it is suggested a penultimate
effect of steric origin is responsible for the decreased selectivity
of the poly(styrene) radical. No significant solvent effect was found
on the reactivity of the 1-phenylethyl radical in the copolymerisation
of methyl methacrylate and maleic anhydride. (C) 1998 Elsevier Scienc
e Ltd. All rights reserved.