A Modular Route for the Synthesis of ABC Miktoarm Star Terpolymers via a New Alkyne-Substituted Diphenylethylene Derivative

We introduce a modular route for the synthesis of well-defined ABC miktoarm star terpolymers. To this aim, the synthesis of a 1,1-diphenylethylene derivative bearing a protected alkyne function (1-[(4-(tert-butyldimethylsilyl)ethynyl)phenyl]-1-phenylethylene) was developed. This compound was for the first time employed in sequential anionic polymerization to readily prepare alkyne mid-functionalized diblock copolymers with polybutadiene as first and a poly(alkyl methacrylate) (poly(tert-butyl methacrylate), poly(N,N-dimethylaminoethyl methacrylate)) as second block. For the third arm controlled radical polymerization methods (polystyrene, poly(tert-butyl methacrylate), poly(N,N-dimethylaminoethyl methacrylate)) and anionic ring-opening polymerization (poly(ethylene oxide)) were used to separately prepare homopolymers with an azido function. Afterward, azide–alkyne Huisgen cycloaddition was successfully employed to synthesize a library of ABC miktoarm star terpolymers with different molecular weights and c...