| Abstract: | Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis revealed that the HCl–vinyl ether adduct/SnCl4/n‐Bu4NCl initiating system induced living cationic polymerization of isobutyl vinyl ether in CH2Cl2 at ?78 °C, that is, the well‐resolved spectra demonstrated that the produced polymers consist of only one series of polymers carrying one initiator fragment at the α end and one methoxy group originated from quenching with methanol at the ω end. The polymer molecular weight as well as the terminal structure were unchanged even when the reaction mixtures were kept unquenched at ?78 °C for an interval of more than five times longer than the reaction period after complete consumption of monomer, which indicates the long lifetime of the living end even under such starved conditions. In contrast, the polymers obtained at a higher temperature, ?15 °C, showed an additional minor series of polymers formed via proton initiation, originating from adventitious water. Under the starved conditions, other side reactions occurred to generate minor series of polymers with an aldehyde ω end or a diisobutyl acetal ω end. Rather surprisingly, however, unsaturated C?C end groups were not detected, which means the absence of β‐proton elimination under these conditions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1249–1257, 2001 |
