Living cationic polymerization of vinyl ethers

Abstract

Abstract:The cationic polymerization of vinyl ethers initiated by CH3-CH(OR)(I) /%N+A-(R = Alkyl, A-= ClO4-. BF4-, PF6-. I-. NO -shows the characteristics of a living polymerization. The rate of polymerization is a function of the solvent polarity, the temperature, the type and concentration of the ammonium salt. The experimental data can be explained on the basis of the secondary salt effect overlapped by some dipol-dipol interactions of the chain end and the added salt. Functionalization of the chain end with thermolabile azo functions yields polymeric initiator which was applied for the synthesis of blockcopolymers. Vinyl ethers functionalized with furylacrylic ester groups were polymerized and crosslinked via [ 2 + 2 ] cycloaddition.

A Renaissance in Living Cationic Polymerization

“…The PIB macroinitiator was used for the radical polymerization of vinyl monomers such as St and MMA to give various block copolymers. As another transformation, polymers with a terminal trityl group or dithiocarbamate were first prepared and subsequently used to initiate radical polymerization of MMA or St via the initer mechanism for the preparation of block copolymers. − On the other hand, polymeric azo compounds were also prepared by the termination of living poly(VE) with an azo-containing alcohol …”