Abstract

AbstractThis study has shown a nearly perfect living polymerization of isobutyl vinyl ether (IBVE) to proceed not only in nonpolar media (e.g., n‐hexane) but in relatively polar CH2Cl2 solvent, provided that the HI concentration is sufficiently high. The produced polymers had a nearly monodisperse molecular weight distribution (Mw/Mn ≤ 1.1); the number‐average molecular weight (Mn) increased in direct proportion to IBVE conversion and its increase continued on the addition of a fresh feed of the monomer at the end of the polymerization. The use of a more polar medium (PhNO2/CH2Cl2) or a lower HI concentration leads to chain transfer reactions, by promoting the ionic dissociation of the “nondissociated” living propagating species. The successful living polymerization by HI/I2 in CH2Cl2 indicates a very strong interaction between the iodide anion and the growing end.

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