Living cationic polymerization of vinyl ethers initiated by electrophilic selenium reagents under ambient conditions

We present a living cationic polymerization of vinyl ethers utilizing electrophilic selenium reagents as initiators and pentacarbonylbromomanganese (Mn(CO)(5)Br) as the catalyst. The polymerization could be carried out under ambient conditions, i.e. no strict purification of reagents, non-inert atmosphere and room temperature. Poly(vinyl ether)s were obtained with controlled molecular weights while maintaining narrow molecular weight distributions (D < 1.2). In this way, different selenium-containing structures could be introduced into chain ends of polymers by using suitable electrophilic selenium reagents. Poly(styrene) prepared by atom transfer radical polymerization (ATRP) followed by brominated selenization was further utilized as a macro-initiator to form the corresponding poly(styrene)-b-poly(isobutyl vinyl ether) copolymers, which offered a new avenue for mechanism transformation polymerization.