One-pot cascade polymerization based on the addition reactions of electrophilic selenium reagents to alkenes

A direct polymerization based on the addition reactions of electrophilic selenium reagents to alkenes was established. It consists of a one-pot cascade process with the generation of selenyl chloride by in situ breakage of the Se-Se bond using sulfuryl chloride, followed by the addition of the obtained selenyl chloride to the carbon-carbon double bond. The polymerization mechanism was confirmed to be a stepwise mechanism. The resulting polymers were characterized and determined to be linear polymers with a sequence regulated backbone repeating unit of ester-selenide-vinyl chloride. When the proportion of sulfuryl chloride was controlled, vinyl terminal groups and diselenide could be easily introduced at the same time, providing a simple way for further modification and application. The feasibility of monomers derived from low cost and easily available unsaturated natural fatty alcohols such as oleyl alcohol, 5-norbornene-2-methanol, etc., was also investigated. It is worth emphasizing specially that the ester-selenide bridged backbone endowed the polyesters with multi stimuli-responsiveness for practical applications.