Synthesis of end‐group functionalized poly(octadecyl vinyl ether)

The cationic polymerization of octadecyl vinyl ether (ODVE) initiated by trimethylsilyl iodide and 1,1-diethoxyethane in the presence of ZnI2 in toluene at 0°C and 10°C has been investigated. For molecular weights lower than 6000, a linearity of M̄n with conversion was observed, but for higher molecular weights a strong deviation from calculated values, assuming a living mechanism, was found. Kinetic analysis of the polymerization and the variation of molecular weight as a function of conversion was in agreement with a transfer to monomer with ktr/kp ≌ 0.006 at 10°C. Analysis of the polymers obtained by termination with methanol provided evidence that the alkenyl ether end-groups formed by the transfer reaction lead to the same acetal end-groups as the active species. As a consequence, it is possible to prepare functionalized polyODVE polymers by end-capping with alcohols. This was confirmed by the synthesis of polyODVE macromonomers by end-capping with 2-hydroxyethyl methacrylate.