A Facile Strategy for Preparation of α ‐Heterobifunctional Polystyrenes with Well‐Defined Molecular Weight

A facile strategy for synthesis of α ‐heterobifunctional polystyrenes is reported. The novel functional polystyrenes have been successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and chemical modification of end‐functional groups. First, ε ‐caprolactone end‐capped polystyrenes with controlled molecular weight and low polydispersity were prepared by ATRP of styrene using α ‐bromo‐ ε ‐caprolactone ( α BrCL) as an initiator. Then, removal of the terminal bromine atom was performed with iso ‐propylbenzene in the presence of CuBr/PMDETA. Finally, ring‐opening modifications of the caprolactone group were carried out with amines, n ‐butanol and H 2 O to produce novel polystyrenes containing two different functional groups at one end.