Abstract
Living cationic polymerization of 2-adamantyl vinyl ether (2-vinyloxytricyclo[3.3.1.1]3,7decane; 2-AdVE) was achieved with the CH3CH(OiBu)OCOCH3/ethylaluminum sesquichloride/ethyl acetate [CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt] initiating system in toluene at 0 °C. The number-average molecular weights (Mn's) of the obtained poly(2-AdVE)s increased in direct proportion to monomer conversion and produced the polymers with narrow molecular weight distributions (MWDs) (Mw/Mn = ∼1.1). When a second monomer feed was added to the almost polymerized reaction mixture, the added monomer was completely consumed and the Mn's of the polymers showed a direct increase against conversion of the added monomer. Block and statistical copolymerization of 2-AdVE with n-butyl vinyl ether (CH2CHOCH2 CH2CH2CH3; NBVE) were possible via living process based on the same initiating system to give the corresponding copolymers with narrow MWDs. Grass transition temperature (Tg) and thermal decomposition temperature (Td) of the poly(2-AdVE) (e.g., Mn = 22,000, Mw/Mn = 1.17) were 178 and 323 °C, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1629–1637, 2008
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