Abstract
AbstractFast living cationic polymerization of isobutyl vinyl ether (IBVE) was examined using the initiating system 1‐(isobutoxy)ethyl acetate (1)/C2H5AlCl2 in the presence of various esters in hexane between 0°C and +40°C. Methyl chloroacetate as added ester turned out to be effective: the apparent polymerization rate constant k was larger by a factor of 400 – 500 than that in the presence of methyl acetate. The rate difference was explained on the basis of the basicity of the esters and their nucleophilic interaction with the propagating species. The polymers obtained in the presence of both esters had a narrow molecular‐weight distribution (MWD) (Mw/Mn ≤ 1,1), and Mn was directly proportional to monomer conversion. As low reactive monomers, 2‐chloroethyl vinyl ether (CEVE) and tert‐butyldimethylsilyl vinyl ether (SiVE) were polymerized under similar conditions. By selecting methyl chloroacetate as an additive, in the case of CEVE, fast living polymerization was achieved to give quantitative conversion within 10 min at 0°C; in the case of SiVE, polymers with a narrow MWD were obtained even at −20°C in high yield, whereas hardly any polymerization of SiVE occurred in the presence of methyl acetate.
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