Design of new polymer architectures by combination of anionic and cationic living polymerization techniques

Abstract The grafting of polystyryl lithium onto poly(chloroethyl vinyl ether) chains has been investigated. The reaction proceeds cleanly and quantitatively thus allowing the synthesis of comblike polymers. Since the dimensions of the polystyrene branches and of the poly(chloroethyl vinyl ether) backbone can be controlled by living polymerizations, both the length and the number of branches of the graft copolymers can be tuned. The latter behave as star polymers. The possibility to initiate a new cationic polymerization of chloroethyl vinyl ether from polystyrene branches bearing acetal termini in order to prepare the corresponding stars with poly(chloroethyl vinyl ether‐b‐ styrene) branches is also examined. Finally access to hyperbranched polymers of controlled architecture and dimensions by deactivation of a second amount of polystyryl lithium onto the last blocks of poly(chloroethyl vinyl ether) is also reported.