Abstract

The anionic polymerization of a series of methacrylates, i.e. methyl methacrylate (MMA), tert-butyl methacrylate (tBuMA), (dimethylamino)ethyl methacrylate (DMAEMA), and glycidyl methacrylate (GMA), has been investigated in THF at −78 °C, by using both lithium diisopropylamide (LDA) and α-lithioethyl isobutyrate (Li-EIB) complexed with LiCl as initiators. Compared to ligated Li-EIB, which is a model for the propagating enolate in the methacrylate anionic polymerization, ligated LDA has quite a comparable initiation efficiency (>90%) and gives rise to polymers with a predictable molecular weight and a narrow molecular weight distribution (MWD < 1.1). The effect of LiCl on the MWD of poly-GMA is less pronounced compared to the other polymethacrylates. An already narrow MWD in the absence of LiCl might be accounted for by an intramolecular coordination of the ion pair by the oxirane group of the (ante)penultimate unit(s) of growing poly GMA. As a direct consequence of the well-controlled anionic polymerizati...

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