Abstract

A mixed complex of a polydentate lithium alkoxide, i.e., lithium 2-(2-methoxyethoxy) ethoxide (LiOEEM), and of a mono- or bisfunctional organolithium initiator, i.e., (diphenylmethyl)lithium (DPMLi) or lithium naphthalene/diphenylethylene, has been used to synthesize well-controlled AB (BA), ABA, and BAB block copolymers of methylmethacrylate (MMA) (A) and 2-ethylhexyl acrylate (2EtHA) (B), irrespective of the monomer addition order. Although the 2EtHA block copolymerization initiated with monofunctional living PMMA macroanions at -78°C in a 75/25 toluene/THF mixture gives rise to a precisely-tailored pMMA-b-P2EtHA diblock polymer,the reverse sequence, i.e., from P2EtHA anions to the MMA type monomer, always results in contamination by homo-P2EtHA

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