Cationic polymerization alpha-methyl vinyl ethers was examined using an IBEA-Et1.5AlCl1.5/SnCl4 initiating system in toluene in the presence of ethyl acetate at 0 similar to-78 degrees C. 2-Ethylhexyl 2-propenyl ether (EHPE) had a higher reactivity, compared to corresponding vinyl ethers. But the resulting polymers had low molecular weights at 0 or -50 degrees C. In contrast, the polymerization of EHPE at -78 degrees C almost quantitatively proceeded, and the number-average molecular weight (M-n) of the obtained polymers increased in direct proportion to the EHPE conversion with quite narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight <= 1.05). In monomer-addition experiments, the M. of the polymers shifted higher with low polydispersity as the polymerization proceeded, indicative of living polymerization. In the polymerization of methyl 2-propenyl ether (MPE), the living-like propagation also occurred under the reaction conditions similar to those for EHPE, but the elimination of the pendant methoxy groups was observed. The introduction of a more stable terminal group, quenched with sodium diethyl malonate, suppressed this decomposition, and the living polymerization proceeded. The glass transition temperature of the obtained poly(MPE) was 34 degrees C, which is much higher than that of the corresponding poly(vinyl ether). This poly(MPE) had solubility characteristics that differed from those of poly(vinyl ethers). (c) 2008 Wiley Periodicals, Inc.