Facile postpolymerization end-modification of RAFT polymers

One-pot methods for the end-group postpolymerization modification of reversible addition fragmentation chain transfer (RAFT) derived polymers were investigated. Dithioester-terminated polymers were transformed into ω-functionalized polymers through conjugate addition of a variety of acrylates with an intermediate thiol. These methods provide a versatile means of introducing a variety of functionalities onto the polymer terminus, while simultaneously removing the residual dithiobenzoate group. A series of functionalized polymethylmethacrylate-b-polystyrene (PMMA-b-PS) polymers were synthesized utilizing the developed methods to probe the effect of charged end groups on diblock copolymer phase separation in thin films.