Anionic polymerization of acrylates. XIV. Synthesis of MMA/acrylate block copolymers initiated with ester-enolate/tert-alkoxide complex

Diblock copolymers of methyl methacrylate (MMA) with 2-ethylhexyl, butyl, ethyl or tert-butyl acrylate (EtHA, BuA, EtA, t-BuA) have been prepared by the ligated anionic polymerization initiated with methyl 2-lithioisobutyrate (MIB-Li) in the presence of an excess of Li tert-butoxide (t-BuOLi) in toluene/THF mixture at −60 or −78 °C. The copolymers, prepared at −60 °C, show MWD with a hint of bimodality, indicating partial deactivation of the living PMMA upon addition of acrylic monomer. At −78 °C, the extent of this deactivation is distinctly lower, the formed block copolymers, in particular, poly(MMA-b-EtHA), have unimodal MWD and exhibit tails only in the lower-molecular-weight region. Poly(MMA-b-EtHA)s were extracted with acetonitrile dissolving PMMA; very small parts of the crude products dissolved, whereas prevailing parts remained as solids documenting thus formation of block copolymer in a high yield. Surprisingly, the highest amount of self terminated PMMA was found in block copolymerization of MMA with t-BuA at both the temperatures, the products of which had clearly bimodal MWDs. This finding is shortly discussed on the basis of relatively slow propagation of t-BuA in comparison with EtHA, BuA and EtA.