Living cationic polymerization of amide‐functional vinyl ethers: Specific properties of SnCl₄‐based initiating system

Abstract

Abstract Living cationic copolymerization of amide‐functional vinyl ethers with isobutyl vinyl ether (IBVE) was achieved using SnCl 4 in the presence of ethyl acetate at 0 °C: the number–average molecular weight of the obtained polymers increased in direct proportion to the monomer conversion with relatively low polydispersity, and the amide‐functional monomer units were introduced almost quantitatively. To optimize the reaction conditions, cationic polymerization of IBVE in the presence of amide compounds, as a model reaction, was also examined using various Lewis acids in dichloromethane. The combination of SnCl 4 and ethyl acetate induced living cationic polymerization of IBVE at 0 °C when an amide compound, whose nitrogen is adjacent to a phenyl group, was used. The versatile performance of SnCl 4 especially for achieving living cationic polymerization of various polar functional monomers was demonstrated in this study as well as in our previous studies. Thus, the specific properties of the SnCl 4 initiating system are discussed by comparing with the Et x AlCl 3− x systems from viewpoints of hard and soft acids and bases principle and computational chemistry. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6129–6141, 2008