Termination of Living Anionic Polymerization of Butyl Acrylate with α‐(Chloromethyl)acrylate for End‐Functionalization and Application to the Evaluation of Monomer Reactivity

Anionic polymerization of n ‐butyl acrylate ( n BA) in toluene initiated with a binary initiator, isopropyl α‐lithioisobutyrate/ethylaluminum bis(2,6‐di‐ tert ‐butylphenoxide) at −60 °C, is terminated with ethyl α‐(chloromethyl)acrylate (ECMA) to afford a poly( n BA) possessing an acryloyl group at the terminal with 80% of termination efficiency. The reactivity of n BA against a polymer anion of methyl methacrylate formed under identical conditions is estimated relative to the termination with ECMA by reacting a mixture of n BA and ECMA followed by 1 H NMR spectroscopic chain‐end analysis; the relative reactivity of n BA is found 80 times or more higher than ECMA.